JP7015791B2 - Manufacture and operation of correlated electronic material devices - Google Patents

Description

The present technique generally relates to correlated electronic devices and, more specifically, to techniques for making correlated electronic devices capable of exhibiting desirable impedance characteristics that can be used in switches, storage circuits and the like.

Integrated circuit devices such as electronic switching devices can be recognized, for example, in a wide variety of electronic device types. For example, the storage device and / or the logical device can incorporate an electronic switch suitable for use in a computer, a digital camera, a smartphone, a tablet device, a portable information terminal, or the like. Factors relating to electronic switching devices may be of interest to the designer when considering whether an electronic switching device is suitable for a particular application, such as physical size, storage density, operating voltage, impedance range and / or power. Consumption can be mentioned. Other factors that the designer may pay attention to include, for example, manufacturing cost, ease of manufacturing, scalability and / or reliability. Moreover, there appears to be an increasing need for storage and / or logic devices that exhibit the characteristics of lower power and / or higher speed. However, while conventional fabrication methods may be well suited for certain types of storage and / or logic devices, they may not be suitable for use in the fabrication of devices that utilize correlated electronic materials.

The claimed subject matter is specifically pointed out and explicitly claimed in the last part of the specification. However, by referring to the detailed description below and reading the accompanying drawings as well, the claimed subject matter, with respect to both the composition of the operation and the method of operation, is the purpose and feature of the claimed subject matter. And / or along with the benefits, can be best understood.

It is explanatory drawing of the current density compared with the voltage profile about the device formed from the correlated electronic material by one Embodiment. It is explanatory drawing of one Embodiment of the switching device including the correlated electronic material, and the schematic diagram of the equivalent circuit of the correlated electronic material switch. It is explanatory drawing of one Embodiment of the switching device containing the filament in the transition metal oxide film formed between the conductive materials. It is explanatory drawing which illustrates the electron donation and back donation through the sigma bond and the π bond of the metal-carbonyl-containing molecule in the correlated electron material by one Embodiment. It is explanatory drawing which illustrates the electron donation and back donation via a sigma bond and a π bond of a metal-carbonyl-containing molecule in a correlated electron material by one Embodiment. It is explanatory drawing which illustrates the electron donation and back donation through the sigma bond and the π bond of the metal-carbonyl-containing molecule in the correlated electron material by one Embodiment. It is explanatory drawing which illustrates the electron donation and back donation through the sigma bond and the π bond of the metal-carbonyl-containing molecule in the correlated electron material by one Embodiment. It is a figure which shows the typical nickel oxide complex which contains the defect of the form of an oxygen empty lattice point in the correlated electron material by one Embodiment which can be filled by the carbonyl molecule of FIGS. 3A-3D. It is a graph which illustrates the energy as opposed to the density of states in the nickel-based correlated electron material by one Embodiment which contains oxygen as a dominant ligand. It is a graph which illustrates the energy as opposed to the density of states in the nickel-based correlated electron material by one Embodiment which contains oxygen as a dominant ligand. It is a flow chart of one Embodiment of the method for manufacturing a correlated electronic material. It is a flow chart of the method for manufacturing the correlated electronic material film by one or more embodiments. It is a flow chart of the method for manufacturing the correlated electronic material film by one or more embodiments. It is a flow chart of the method for manufacturing the correlated electronic material film by one or more embodiments. FIG. 6 is a diagram of a bis (cyclopentadienyl) molecule (Ni (C ₅ H ₅ ) ₂ ) that can serve as an exemplary precursor of a gaseous form used in the fabrication of correlated electronic material devices according to one embodiment. It is a figure which shows the subprocess used in the method for making a film mainly containing NiO including the correlated electronic material device by one Embodiment. It is a figure which shows the subprocess used in the method for making a film mainly containing NiO including the correlated electronic material device by one Embodiment. It is a figure which shows the subprocess used in the method for making a film mainly containing NiO including the correlated electronic material device by one Embodiment. It is a figure which shows the subprocess used in the method for making a film mainly containing NiO including the correlated electronic material device by one Embodiment. It is a figure which shows the precursor flow rate and temperature profile according to the time which can be used in the method for manufacturing the correlation electronic device material by one Embodiment of the device mainly made of NiO. It is a figure which shows the precursor flow rate and temperature profile according to the time which can be used in the method for manufacturing the correlation electronic device material by one Embodiment of the device mainly made of NiO. It is a figure which shows the precursor flow rate and temperature profile according to the time which can be used in the method for manufacturing the correlation electronic device material by one Embodiment of the device mainly made of NiO. It is a figure which shows the precursor flow rate and temperature profile according to the time which can be used in the method for manufacturing the correlation electronic device material by one Embodiment of the device mainly made of NiO. It is a figure which shows the precursor flow rate and temperature profile with time which can be used in the method for making a correlated electronic device material by one Embodiment. It is a figure which shows the precursor flow rate and temperature profile with time which can be used in the method for making a correlated electronic device material by one Embodiment. It is a figure which shows the precursor flow rate and temperature profile with time which can be used in the method for making a correlated electronic device material by one Embodiment. It is a figure which shows the precursor flow rate and temperature profile with time which can be used in the method for making a correlated electronic device material by one Embodiment. It is a figure which shows the temperature profile according to the time used in the deposition process and the annealing process for manufacturing the correlated electronic material device by one Embodiment. It is a figure which shows the temperature profile according to the time used in the deposition process and the annealing process for manufacturing the correlated electronic material device by one Embodiment. It is a figure which shows the temperature profile according to the time used in the deposition process and the annealing process for manufacturing the correlated electronic material device by one Embodiment. It is a flow chart of the method for manufacturing the correlated electronic material film using the nitrogen-containing molecule by one or more embodiments. It is a flow chart of the method for manufacturing the correlated electronic material film using the nitrogen-containing molecule by one or more embodiments. It is a flow chart of the method for manufacturing the correlated electronic material film using the nitrogen-containing molecule by one or more embodiments. FIG. 6 is a diagram of nickel aminate that can function as a precursor used in the fabrication of correlated electronic material devices according to one embodiment. FIG. 6 is a diagram of nickel 2-aminopenta-2-en-4-onato (Ni (apo) ₂ ), which can function as a precursor used in the fabrication of correlated electronic material devices according to one embodiment. It is a figure which shows the subprocess used in the method for making a correlated electronic material device by one Embodiment. It is a figure which shows the subprocess used in the method for making a correlated electronic material device by one Embodiment. It is a figure which shows the subprocess used in the method for making a correlated electronic material device by one Embodiment. It is a figure which shows the subprocess used in the method for making a correlated electronic material device by one Embodiment. FIG. 6 is a flow chart of an embodiment for a further method for making correlated electronic materials. FIG. 6 is a flow chart of an embodiment for a further method for making correlated electronic materials. FIG. 6 is a flow chart of an embodiment for a further method for making correlated electronic materials. FIG. 6 is a flow chart of an embodiment for a further method for making correlated electronic materials. FIG. 6 is a flow chart of an embodiment for a further method for making correlated electronic materials.

In the detailed description below, references are made to the accompanying drawings that form part of this specification, and the corresponding and / or similar numbers may specify similar elements throughout. It will be appreciated that the drawings are not always drawn to a certain scale due to the simplicity and / or clarity of the illustrations and the like. For example, the dimensions of some embodiments may be expanded relative to other embodiments. Furthermore, it should be understood that other embodiments may be utilized. Moreover, structural changes and / or other changes can be made without departing from the claimed subject matter. Throughout this specification, reference to "claimed subject matter" refers to a subject matter intended to be contained by one or more claims or any part of such claim, not necessarily a complete set of claims. , Is not necessarily intended to refer to a particular combination of claims (eg, method claims, device claims, etc.) or a particular claim. Instructions and / or references such as, for example, above, below, top and bottom, etc. are not intended to be used to facilitate the discussion of the drawings and to limit the application of the claimed subject matter. It should also be noted. Therefore, the detailed description below should not be construed to limit the claimed subject matter and / or equivalent.

Throughout this specification, references to one implementation, one implementation, one embodiment and / or one embodiment, etc., are specific features, structures and / or specific features, structures and / or descriptions of a particular implementation and / or embodiment. Or characteristics, etc. are meant to be included in at least one implementation and / or embodiment of the claimed subject matter. Thus, for example, the appearance of such terms in various places throughout the specification does not necessarily refer to or describe the same implementation and / or embodiment of any one particular implementation and /. Or it is not necessarily intended to refer to an embodiment. Moreover, the particular features, structures and / or properties described may be combined with one or more implementations and / or embodiments by various methods and thus the intended claims. It should be understood that it is included in the scope. In general, of course, these objects of interest and other objects of interest may differ in certain contexts of use, as was the case with the specification of one patent application. In other words, throughout this disclosure, certain contexts of description and / or use provide useful guidance regarding rational reasoning to be derived. However, "in this regard" generally refers similarly to the context of the present disclosure, without further requirement.

A particular embodiment of the present disclosure prepares and / or manufactures a correlated electron material (CEM) film, eg, a correlated electron random access memory (CERAM) in a correlated electron switch, eg, a storage device and / or a logical device. Describes methods and / or processes for forming correlated electron switches that can be utilized to form. Correlated electronic materials that can be used in the construction of, for example, CERAM devices and CEM switches are diverse, such as memory controllers, memory arrays, filter circuits, data converters, optics, phase lock loop circuits and microwave and millimeter wave transceivers. Other types of electronic circuits may be included, but the patented subject matter is not limited in these respects. In this regard, for example, a CEM switch can show a fairly rapid transition from conductor to insulator, which transition is, for example, a change from crystalline to amorphous state in a phase change storage device, or another example. In response to the formation of filaments by nanoionics in resistance random access memory (RERAM) devices, etc., it can be brought about by electron correlation rather than structural phase change in the solid state. In one embodiment, the substantially rapid transition from conductor to insulator in a CEM device is significantly different from, for example, phase change and melting / solidification by melting / solidification or nanoionics filament formation in (RERAM) devices, and is a quantum mechanical phenomenon. Quantum mechanical phenomenon) can respond. For example, in CEM, such a quantum mechanical transition between a relatively conductive state and a relatively insulating state and / or between a first impedance state and a second impedance state is It can be understood in any one of several embodiments. As used herein, the terms "relatively conductive state", "relatively lower impedance state" and / or "metal state" can be interchangeable. And / or sometimes referred to as "relatively lower conductivity / impedance". Similarly, the terms "relatively insulating state" and "relatively higher impedance state" can be used interchangeably herein and / or occasionally relative. It is also called "a state where the insulation / impedance is higher".

When the relatively low conductivity / impedance state is substantially different from the higher insulation / impedance state, the relatively higher insulation / impedance state and the relatively conductive / impedance state are used. The quantum mechanical transition of the correlated electronic material with the lower state can be understood in terms of the Mott transition. According to the Mott transition, a material can switch from a relatively higher insulating / impedance state to a relatively lower conductive / impedance state when the Mott transition condition occurs. The Mott reference can be expressed by (n _c ) ^1/3 a≈0.26 (in the equation, n _c represents the electron concentration and "a" represents the Bohr radius). It is believed that a Mott transition occurs when the threshold carrier concentration is achieved such that the Mott criteria are met. In response to the occurrence of the Mott transition, the state of the CEM device is from a relatively higher resistance / higher capacitance state (eg, insulation / higher impedance state) to a higher resistance / higher capacitance state. It changes to a relatively low resistance / low capacitance state (eg, low conductivity / low impedance state), which is substantially different from the high state.

The Mott transition can be controlled by electron localization. For example, when carriers such as electrons are localized, it is considered that strong Coulomb interaction between carriers splits the CEM band, resulting in a relatively insulating state (relatively higher impedance). Has been done. If the electrons are no longer localized, weak Coulomb interactions can predominate, which can eliminate band splitting, which results in relatively higher impedance (insulation). ) State can result in a transition to a metallic (conductive) state (a state with a relatively lower impedance) that is substantially different from the state. Such a transition from a metallic state to an insulating state is further presented and described herein with respect to FIGS. 4A and 4B.

Further, in one embodiment, switching from a relatively higher insulating / impedance state to a substantially different state with a lower relative conductivity / impedance is a change in resistance as well as a change in capacitance. Changes can also be brought about. For example, a CEM device can exhibit variable resistance along with the characteristics of variable capacitance. In other words, the impedance characteristics of a CEM device may include both components relating to resistance and components relating to capacitance. For example, in the metallic state, the CEM device can contain a relatively low electric field that can be close to 0 and thus can exhibit a fairly low capacitance that can also be close to 0.

Similarly, at higher insulation / impedance, which can be brought about by higher density bound or correlated electrons, the external electric field can penetrate the CEM, thus the CEM is in the CEM. Higher capacitance can be shown, at least partially based on the additional charge stored. Thus, for example, the transition from a relatively higher insulating / impedance state in a CEM device to a substantially different state with a lower relative conductivity / impedance is, at least in certain embodiments, of resistance. It can cause both changes and changes in capacitance. Such transitions can result in additional measurable phenomena, but the claimed subject matter is not limited in this regard.

In one embodiment, a device formed from a CEM can exhibit impedance state switching in response to a Mott transition in most of the volume of the CEM constituting the device. In one embodiment, the CEM may form a "bulk switch". As used herein, the term "bulk switch" refers to the volume of at least a majority of the CEM switching the impedance state of the device, such as in response to a Mott transition. For example, in one embodiment, a significant portion of the CEM of a device may switch from a relatively high insulation / impedance state to a relatively low conductivity / impedance state in response to a Mott transition. It is possible, or it is possible to switch from a state where the conductivity / impedance is relatively low to a state where the insulation / impedance is relatively high. In one embodiment, the CEM is one or more transition metals, one or more transition metal compounds, one or more transition metal oxides (TMOs), one or more oxides containing rare earth elements 1. One or more oxides of one or more periodic table d-block or f-block elements may contain one or more rare earth transition metal oxides perovskite, ittrium and / or itterbium, but patent claims The subject matter given is not limited in scope in this regard. In one embodiment, the CEM device is aluminum, cadmium, chromium, cobalt, copper, gold, iron, manganese, mercury, molybdenum, nickel, palladium, rhenium, ruthenium, silver, tantalum, tin, titanium, vanadium, ittrium and zinc. (These may be attached to anions such as oxygen or other types of ligands.) Or may contain one or more materials selected from the group comprising combinations thereof. The claimed subject matter is not limited in scope in this regard.

FIG. 1A is an explanatory diagram of Embodiment 100 with respect to a current density as opposed to a voltage profile of a device formed from correlated electronic materials. The CEM device can be transformed into a relatively low impedance state or a relatively high impedance state, for example during a "write operation", based at least in part on the voltage applied to the terminals of the CEM device. For example, the application of a voltage V _set and a current density J _set can result in a transition of the CEM device to a memory state with relatively low impedance. Conversely, the application of a voltage V _reset and a current density J _reset can result in a transition of the CEM device to a memory state with relatively high impedance. As shown in FIG. 1A, reference number 110 illustrates the voltage range in which the V _set can be separated from the V _reset . After changing the CEM device to a high impedance or low impedance state, certain states of the CEM device apply a voltage V read (eg, during a read operation) and apply a voltage V _read (eg, read window 107). It can be detected by detecting the current or current density at the terminal of the CEM device.

According to one embodiment, the CEM device characterized in FIG. 1A is any transition metal oxide (TMO) such as a perovskite, a Mott insulator, a charge exchange insulator and an Anderson disorder insulator. May include. In certain embodiments, the CEM device is a nickel oxide, cobalt oxide, iron oxide, yttrium oxide, yttrium oxide and perovskite such as chromium-doped strontium titanate, lanthanum titanate and placeodium manganate calcium manganate. And can be formed from switching materials such as the manganate series containing placeodyl lanthanum manganate. In particular, oxides incorporating elements with incomplete "d" and "f" orbital shells can exhibit sufficient impedance switching properties for use in CEM devices. Other implementations can utilize other transition metal compounds without departing from the claimed subject matter.

The CEM device of FIG. 1A may include other types of transition metal oxide variable impedance materials, but these are merely exemplary and are intended to limit the claimed subject matter. You should understand that it is not. Nickel oxide (NiO) is disclosed as a particular type of TMO that constitutes an oxygen-dominated ligand. Therefore, in this regard, the "dominant ligand" referred to herein is most in transition metal oxides or other types of transition metals, d-block-based CEMs or f-block-based CEMs. It means a ligand generated at a high atomic concentration. For example, in a nickel oxide-based CEM that constitutes the dominant ligand, the atomic concentration of oxygen can exceed, for example, approximately 90.0%. However, it should be understood that this is merely an example of a dominant ligand and the claimed subject matter is not limited in this regard.

The CEMs discussed herein may be doped with "extrinsic" or "substituted" ligands that can ensure and / or stabilize variable impedance properties, eg, across CEM films. .. In this regard, the "substituent" ligand referred to herein is the dominant configuration in transition metal molecules or other types of transition metals, d-block-based CEMs or f-block-based CEMs. It means a ligand that can replace a coordinate. For example, in a NiO-based CEM, the carbonyl (CO) molecule can replace the oxygen atom, which increases the conductivity of the CEM operating in a low impedance state. In another example, in a NiO-based CEM, the ammonia (NH ₃ ) molecule can replace the oxygen atom, which also increases the conductivity of the CEM operating at low impedance. do. At least in certain embodiments, possible attributes with respect to the substituted ligand exert an additional function of filling or substituting empty lattice points, such as oxygen empty lattice points, in the coordination sphere of the molecules that make up the CEM. May include doing. In this regard, the "coordination sphere" referred to herein means a central atom or central ion of a particular molecular structure and an atom or molecule directly bonded to the central atom or central ion. A non-limiting example of the "coordination sphere" is shown in FIG. 3E.

In this regard, the "CEM film" referred to herein means a layer comprising one or more elements of the "d" or "f" groups of the Periodic Table of the Elements. One attribute for such an element is a partially filled "d" or "f" atomic orbital, in which such an element is the dominant ligand and substitution type (eg, dopant) coordination. The ability to form a coordination sphere with a child. In this regard, when the term "layer" is used herein, the "layer" can be placed on or over the formation located beneath the substrate or the like. Means a sheet or coating made of a material. For example, a layer deposited on the underlying substrate by the atomic layer growth process can occupy the thickness of a single atom, occupying a fraction of the angstrom (eg, 0.6 Å) thickness. However, the layer includes a sheet or coating having a thickness greater than the thickness of a single atom, depending, for example, depending on the method used to make the multiple films constituting one CEM film.

In some embodiments, the substitution or filling of oxygen empty lattice points, for example with a substituted ligand, is, for example, a change from a crystalline state to an amorphous state in a phase change memory device, or, in another example, a resistance changing type. It is believed that the occurrence of filament formation during CEM is reduced in response to the formation of filaments by nanoionics in RAM (RERAM) devices. Further, for example, substitution or filling of oxygen empty lattice points with a substituted ligand is thought to reduce the occurrence of electron capture in the CEM, which reduces the capacitance of the parasitic device and makes the device durable. Can work to increase. However, it should be understood that the use of substituted ligands can affect other aspects of CEM and the claimed subject matter is not limited in this regard. In multiple embodiments, the substituted ligand may occupy an atomic concentration in the range of approximately 0.1% to 10.0%. As referred to herein, the term atomic concentration generally refers to the concentration of a particular type of atom in the finished material. For example, the atomic concentration of carbon in units of percentage is the total number of carbon atoms contained in the finished material divided by the total number of atoms in the finished material and multiplied by 100. The atomic concentration of a molecular dopant is the atomic concentration of the atom coordinated to the metal in the molecular dopant, that is, the atomic concentration of carbon in the case of a dopant that interacts via carbon such as carbonyl and cyanide, azide, and ammonia. , Atomic concentration of nitrogen in the case of nitrogen-mediated dopants such as ethylenediamine and 1,10 ^- phenanthroline, and the atom of sulfur in the case of sulfur-mediated dopants such as S2- and isothiocyanate. Concentration, refers to the atomic concentration of oxygen in the case of dopants that interact via oxygen, such as water, hydroxides and oxalates. However, it should be understood that the substituted ligands are provided merely as an example, along with exemplary concentrations, and the claimed subject matter is not limited in this regard.

Thus, in another particular example, the substituted ligand-doped NiO is a ligand element or compound such as NiO: L _x (where L is carbonyl (CO) or ammonia (NH ₃ )). Can be indicated, and x can indicate the number of units of the ligand for one unit of NiO.). The value of x can be determined simply by balancing the valences for any particular ligand and ligand with any particular combination of NiO or any other transition metal compound. .. In addition to CO and NH ₃ , other substituted ligands that can function as molecular dopants include nitrosyl (NO), triphenylphosphine (PPh ₃ ), phenanthroline (C ₁₂ H ₈ N ₂ ), bipyridine (C). ₁₀ H ₈ N ₂ ), ethylene (C ₂ H ₄ ), ethylene diamine (C ₂ H ₄ (NH ₂ ) ₂ ), acetonitrile (CH ₃ CN), fluorine (F), chlorine (Cl), bromine (Br), Ethylene, cyanide (CN), sulfur (S), selenium (Se), tellurium (Te) and sulfoselenide (S _x Se _1-x ), sulfosyanide (SCN) and the like can be mentioned.

In another embodiment, the CEM device of FIG. 1A may include other transition metal oxide type variable impedance materials such as nitrogen-containing ligands, but these are only exemplary and patented. It should be understood that it is not intended to limit the claimed subject matter. Nickel oxide (NiO) is disclosed as a specific type of TMO. The NiO materials discussed herein may be doped with a substituted nitrogen-containing ligand capable of stabilizing variable impedance properties. In particular, the NiO variable impedance materials disclosed herein include, for example, ammonia (NH ₃ ), cyano (CN ⁻ ), azide ion (N ₃ ⁻ ), ethylenediamine (C ₂ H ₈ N ₂ ), phen (1). , 10-phenanthroline) (C ₁₂ H ₈ N ₂ ), 2,2'-bipyridine (C ₁₀ H ₈ N ₂ ), ethylenediamine ((C ₂ H ₄ (NH ₂ ) ₂ ), pyridine (C ₅ H ₅ N) ), Ammonia (CH ₃ CN) and cyanosulfanide, such as thiocyanate ( ^NCS- ), nitrosonium (NO), isocyanide ( ^RNC- . Organic fragment (R)) is a functional group N≡ bonded to the isocyanide group by a nitrogen atom. _{C _ _} _ _ _ Includes) nitrogen-containing molecules. The NiO variable impedance materials disclosed herein include an oxygen nitride series (N _x O _y . In the equation, x and y include integers and x. ≧ 0 and y ≧ 0, where at least x or y contains a larger value), although components of these oxygen nitride series may include, for example, nitrogen monoxide (NO). , Nitrogen sulfite ( _N2 O), Nitrogen dioxide (NO ₂ ), or NO ₃ ^- ligon-bearing precursors. In some embodiments, the metal precursors valence. It contains nitrogen-containing ligands such as amines, amides, and alkylamide nitrogen-containing ligands that have become ligands for NiO when combined.

According to FIG. 1A, when sufficient bias is applied (eg, to exceed the band splitting potential (U = ionization-electron affinity) further described for FIGS. 4A and 4B) and the Mott condition is met. (For example, when the injected holes are, for example, a group equivalent to a group of electrons in the switching region), the CEM device responds, for example, to a Mott transition, from a relatively low impedance state to a relative impedance. Can transition to a high state. This may correspond to point 108 of the voltage as opposed to the current density profile of FIG. 1A. At this point 108, or more appropriately near this point 108, the electrons are no longer shielded and become localized near the metal ions. This correlation can result in a strong electron-electron interaction potential, which can act to split the band to form a material with relatively high impedance. If the CEM device contains relatively high impedance conditions, current can be generated by the transport of holes. Therefore, when a threshold voltage is applied across the terminals of a CEM device, electrons can be injected into a metal-insulator-metal (MIM) diode beyond the potential barrier of the MIM device. In certain embodiments, a "set" operation can be performed that transforms the CEM device into a low impedance state by injecting electrons with a threshold current at the threshold potential applied between the ends of the terminals of the CEM device. .. In the low impedance state, the increase in electrons can shield the inflowing electrons and eliminate the localization of the electrons, which disrupts the band splitting potential, thereby resulting in a low impedance state. Can work with.

According to one embodiment, the current in the CEM device can be controlled by externally applied "compliance" conditions that can be determined at least in part based on the applied external current. Can be limited to during the write operation, for example to change the CEM device to a relatively high impedance state. This externally applied compliance current can also, in some embodiments, set current density conditions for subsequent reset operations that transform the CEM device into a relatively high impedance state. As presented in the particular implementation of FIG. 1A, current density J _compliance can be applied at point 116 during write operation to change the CEM device to a relatively low impedance state, followed by. It is possible to determine the compliance conditions for changing the CEM device to a high impedance state in the writing operation of. As presented in FIG. 1A, the CEM device can subsequently be changed to a higher impedance state by applying a current density J _reset > J _compliance at point 108 with a voltage V _reset . J _compliance is applied from the outside.

In multiple embodiments, compliance can set some electrons in the CEM device that can be "captured" by holes for Mott transitions. In other words, the current applied during the write operation to change the CEM device to a relatively low impedance memory state should be injected into the CEM device to transition the CEM device to a relatively high impedance memory state. The number of holes can be determined.

As pointed out above, the reset condition can occur in response to the Mott transition at point 108. As pointed out above, such a Mott transition results in conditions within a CEM device similar to a P-type doped semiconductor, where the electron concentration n is approximately equal to or at least equal to the hole concentration p. Can be done. This condition is based on the following equation (1).

Can be modeled according to.

In equation (1), λ _TF corresponds to the Thomas-Fermi shielding distance, and C is a constant.

According to one embodiment, the current or current density in the region 104 of the voltage compared to the current density profile shown in FIG. 1A is a hole from the voltage signal applied between the ends of the terminals of the CEM device. May be present in response to an infusion of. Here, when the threshold voltage _VMI is applied between both ends of the terminals of the CEM device, the hole injection satisfies the Mott transition criterion for transitioning from a low impedance state to a high impedance state in the current _IM . be able to. This is based on the following equation (2)

(In the equation, Q ( _VMI ) corresponds to the injected charge (hole or electron) and is a function of the applied voltage.)
Can be modeled according to. Injection of electrons and / or holes to allow the Mott transition can occur between bands in response to the threshold voltage V _MI and the threshold current I _MI . Thus to the Thomas Fermi shielding distance λ _TF by equalizing the electron concentration n to the charge concentration and resulting in a Mott transition due to the holes injected by the _IM in equation (2) according to equation (1). The dependence of the threshold voltage _VMI is based on the following equation (3).

(In the equation, _ACEM is the cross-sectional area of the CEM device and J _reset (VMI) is applied to the CEM device at the threshold voltage _VMI which can change the CEM device to a relatively high impedance state. Can represent the current density throughout the CEM device.)
Can be modeled according to.

FIG. 1B is an explanatory diagram of an embodiment 150 of a switching device including a correlated electronic material and a schematic diagram of an equivalent circuit of a correlated electronic material switch. As mentioned above, correlated electronic devices such as CEM switches, CERAM arrays or other types of devices that utilize one or more correlated electronic materials can exhibit both variable resistance and variable capacitance characteristics. Variable or complex impedance devices may be included. In other words, the impedance characteristics for a CEM variable impedance device, such as a device containing a conductive substrate 160, CEM 170 and a conductive overlay 180, will be the resistance and capacitance characteristics of the device when measured between the device terminals 122 and 130. It can be at least partially dependent. In one embodiment, the equivalent circuit for a variable impedance device may include a variable resistor such as a variable resistor 126 that is parallel to a variable capacitor such as the variable capacitor 128. Of course, the variable resistor 126 and the variable capacitor 128 are shown in FIG. 1B as including separate components, but variable impedance devices such as the device of embodiment 150 have a substantially uniform CEM. The subject matter, which may be included, is not limited in this regard.

Table 1 below illustrates an exemplary truth table for exemplary variable impedance devices such as the device of embodiment 150.

In one embodiment, Table 1 shows that the resistance of a variable impedance device, such as the device of embodiment 150, is at least partially dependent on the low impedance state and the voltage applied across the CEM device. It shows that the functionally different impedances can transition to and from the high state. In one embodiment, the impedance shown in the low impedance state is in the range of approximately 10.0 to 100,000,000 compared to the substantially different impedance shown in the high impedance state. possible. In other embodiments, the impedance shown in the low impedance state can be, for example, in the range of approximately 5.0 to 10.0 times as compared to the impedance shown in the high impedance state. However, it should be noted that the claimed subject matter is not limited to any particular impedance ratio between the high impedance state and the low impedance state. Table 1 shows that the capacitance of a variable impedance device, such as the device of embodiment 150, may have a capacitance of approximately 0 (or very small) in one exemplary embodiment, with a lower capacitance and at least partial. Shows that the capacitance, which is a function of the voltage applied across the CEM device, can transition to a higher state.

According to one embodiment, a CEM device, a CERAM storage device or various other electronic devices including one or more correlated electronic materials that can be utilized to form a CEM switch are, for example, to meet the Mott transition criteria. By injecting a sufficient amount of electrons, it is possible to change from a state where the impedance is relatively high to a memory state where the impedance is relatively low. Injecting enough electrons when transitioning the CEM device to a relatively low impedance state and when the potential between the terminals of the CEM device exceeds the threshold switching potential (eg V _set ). The resulting electrons can initiate shielding. As mentioned above, shielding can act to delocalize the double occupied electrons and disrupt the band splitting potential (U), thereby resulting in a relatively low impedance state.

In a particular embodiment, changes in the impedance state of a CEM device, such as a change from a low impedance state to a substantially different high impedance state, are transition metals, transition metal oxides (Ni _{x Oy} , etc.). The middle, subscripts "x" and "y" can be brought about by "donating" and "reverse donating" electrons in a material containing a), d-block metal or f-block metal. In this regard, when the term electron "donation" is used herein, electron "donation" is, for example, a transition metal, transition metal, as described in more detail with respect to FIGS. 3A-3D. One to transition metals, transition metal oxides, d-block metals or f-block metals or any combination thereof by adjacent molecules in the coordination zone containing oxides, d-block metals or f-block metals or combinations thereof. Or it means the supply of multiple electrons. When the term "back-donation" of an electron is used herein, the "back-donation" of an electron is, for example, dominant or substituted, as also described in more detail with respect to FIGS. 3A-3D. Refers to the acceptance of one or more electrons by adjacent molecules in the coordination sphere containing type ligands. By donating and back-donating electrons, transition metals, transition metal compounds, transition metal oxides, d-block metals or f-block metals or combinations thereof can maintain an ionized state in which the impedance can be controlled under the influence of the applied voltage. It is possible. In certain embodiments, donations and reverse donations, eg, in CEM, are carbon-containing dopants such as carbonyl (CO), or eg ammonia (NH ₃ ), ethylenediamine (C ₂ H ₈ N ₂ ) or oxynitride series ( It is possible to enhance in response to the use of nitrogen-containing dopants such as N _{x Oy} ) components, which allow the CEM to, for example, during the operation of a device or circuit containing the CEM, such as nickel. It is possible to exhibit the property of reversibly donating electrons to the conduction band of a transition metal or a transition metal oxide in a controllable manner. In some embodiments, the donation can be reversed, for example in a nickel oxide material (eg, NiO: CO or NiO: NH ₃ ), which allows the nickel oxide material to exhibit high impedance characteristics during device operation. It is possible to transition from the state shown to the state showing low impedance characteristics. Therefore, in this regard, the donor / backdonant material is at least partly affected by the applied voltage for controlling electron donation and electron donation reversal (backdonation) with the conduction band of the material as the end and start points. From a first impedance state to a second impedance state that is substantially different (eg, from a relatively low impedance state to a relatively high impedance state, or vice versa). Refers to materials that exhibit impedance switching characteristics, such as switching).

As described in more detail with respect to FIGS. 4A and 4B, by electron donation, a CEM switch containing a transition metal, a transition metal compound or a transition metal oxide is such that the transition metal such as nickel is in a 2+ oxidation state (eg, for example). When the material is changed to Ni ²⁺ .NiO: CO or NiO: NH ₃ etc.), low impedance characteristics / low capacitance characteristics can be exhibited. Conversely, electron donation can be reversed if a transition metal such as Ni changes to a 1+ or 3+ oxidation state. Therefore, during the operation of the CEM device, backbonding can cause "disproportionation", which is expressed by the following equation (4).
2Ni ²⁺ → Ni ¹⁺ + Ni ³⁺ (4)
May include substantially simultaneous oxidation and reduction reactions according to.

In the above case, such disproportionation can result in, for example, a relatively high impedance state during operation of the CEM device, of the nickel ions as Ni ¹⁺ + Ni ³⁺ represented by equation (4). Refers to formation. The electron donation is given by the following formula (5).
Ni ¹⁺ + Ni ³⁺ → 2Ni ²⁺ (5)
It is possible to cause the reversal of the disproportionation reaction of the equation (4) substantially according to.

In this regard, the "molecular dopant" referred to herein is a coordination of a CEM with a transition metal, a transition metal oxide, a d-block-based metal or an f-block-based metal constituting the CEM as an end point or a starting point. It means an atomic or molecular species that enables local electron donation or back donation such as in the sphere. Therefore, in the coordination sphere, the donation of electrons from the molecular dopant to the metal can result in a low impedance state of the CEM. Further, in the coordination sphere, the back donation of electrons from the metal to the molecular dopant can result in a high impedance state of the CEM. In one embodiment, a "molecular dopant" such as a carbon-containing ligand (eg, CO) or a nitrogen-containing ligand (eg, NH ₃ ) is a disproportionation and non-uniformization of formulas (4) and (5). It may allow electron sharing during operation of the CEM device so as to reverse the averaging.

As described with respect to FIGS. 3A-3D, certain molecular dopants, including specific molecules such as CO and NH ₃ , donate electrons, for example from sigma bonds, locally to the coordination sphere. Or work in the coordination sphere. In one embodiment, such a sigma bond can be formed between a carbon and an oxygen atom and can back-donate an electron from the π bond of the metal atom. Without being bound by theory, molecular dopants act locally on the coordination sphere of the CEM to donate and / or back electrons, halides (eg, Cl, Br, F, etc.). Further include specific monoatomic species such as. The donation of electrons in the molecularly doped CEM acts to reduce the energy gap between the conduction band and the valence band of the metal atom in the coordination zone, whereas the reverse donation of electrons in the molecularly doped CEM acts in the coordination band. It can act to increase the energy between the conduction band and the valence band of the metal ions in it. Illustrative theoretical behavior of monoatomic molecular dopants is described with respect to FIGS. 4A and 4B.

In this regard, the "sigma bond" referred to herein means a chemical covalent bond formed by the overlap of the axes of atomic orbitals. For example, in a CO molecule, a sigma bond refers to an electron that can be "shared" between a carbon atom and an oxygen atom. However, it should be understood that this is merely an example of sigma bonds and the claimed subject matter is not limited in this regard. Further, in this regard, the "π bond" referred to herein means a covalent bond resulting from the formation of a molecular orbital by overlapping the atomic orbitals of the participating atoms side by side. For example, in a CO molecule, the π bond refers to the orbital of the CO molecule from side to side, as given by 322 and 324 in FIGS. 3A and 3B. However, it should be understood that this is an example of pi bonds and the claimed subject matter is not limited in this regard.

CO, NH ₃ , Cl, Br and F are merely examples of molecular dopants, such as cyano (CN-), azide ion ( _N3- ⁾ , ^{ethylenediamine} _{( C2H8N2} ), phen ₍ 1,10). -Phenanthroline) (C ₁₂ H ₈ N ₂ ), 2,2'-bipyridine (C ₁₀ H ₈ N ₂ ), ethylenediamine ((C ₂ H ₄ (NH ₂ ) ₂ ), pyridine (C ₅ H ₅ N), Other types of molecular dopants such as acetonitrile (CH ₃ CN) and cyanosulfanides can also provide electron donation or back donation to operate the CEM in low and high impedance conditions. It should be understood that the claimed subject matter is not limited in this regard.

In a plurality of embodiments, the concentrations of molecular dopants such as carbonyl (which will form NiO: CO) and ammonia (which will form NiO: NH ₃ ) are approximately 0.1% to 10.0. It can be an atomic percentage value in the range of%. Such concentrations can affect V- _reset and V- _set , as shown in FIG. 1A, where V- _reset and V- _set are approximately 0.1V to 10.0V depending on the condition that V- _set ≥ V- _reset . It can be a range of ranges. For example, in one possible embodiment, for example, a V _reset can occur at a voltage in the range of approximately 0.1V to 1.0V and a V _set can occur at a voltage in the range of approximately 1.0V to 2.0V. .. However, changes in V- _set and V- _reset can vary, such as changes in the atomic concentrations of donor or backdonant materials such as NiO: CO or NiO: _NH3 and other materials present in the CEM device, as well as in other processes. It should be noted that the claimed subject matter is not limited in this regard, although it can occur at least in part based on the elements of.

In certain embodiments, atomic layer deposition (ALD) is used to form or fabricate a film containing a NiO material such as NiO: CO or NiO: NH ₃ , which results in, for example, low impedance / low capacitance. May allow electron donation during operation of the CEM device in a circuit environment. For example, even during operation in a circuit environment, electron donation can be reversed to produce substantially different impedance states, such as high impedance states. In certain embodiments, atomic layer deposition utilizes two or more precursors to conduct, for example, NiO: CO or NiO: NH ₃ or other transition metal oxides, transition metals or components of combinations thereof. It can be deposited on a substrate. In one embodiment, the layer of the CEM device is the following formula (6a).
AX _(gas) + BY _(gas) = AB _(solid) + XY _(gas) (6a)
(In the formula, "A" in formula (6a) corresponds to a transition metal, a transition metal compound, a transition metal oxide or any combination thereof), utilizing separate precursor molecules AX and BY. Can be deposited. In some embodiments, the transition metal oxide may include nickel, but aluminum, cadmium, chromium, cobalt, copper, gold, iron, manganese, mercury, molybdenum, nickel, palladium, renium, ruthenium, silver. , Tantal, tin, titanium, vanadium, ittrium and zinc (which may be attached to anions such as oxygen or other types of ligands) or transition metals such as transition metals, transition metal compounds and combinations thereof. / Or may contain other metals such as transition metal oxides, however, the claimed subject matter is not limited in scope in this regard. In certain embodiments, compounds containing more than one transition metal oxide, such as yttrium titanate (YTIO ₃ ), may be utilized.

In a plurality of embodiments, the "X" in formula (6a) may comprise one or more ligands, such as an organic ligand, and an aminate (AMD, eg, [RNCR ¹ NR ² ] ^- . (In the formula, R, R ¹ and R ² are selected from H or alkyl)), di (cyclopentadienyl) (Cp) ₂ , di (ethylcyclopentadienyl) (EtCp) ₂ , bis ( 2,2,6,6-tetramethylheptane-3,5-dionat) ((thd) ₂ ), acetylacetonate (acac), bis (methylcyclopentadienyl) ((CH ₃ C ₅ H ₄ ) ₂ ) ), Dimethylglycimate (dmg) ₂ , 2-Amino-penta-2-en-4-onato (apo) ₂ , (dmamb) ₂ (In the formula, dmamb is 1-dimethylamino-2-methyl-2. -Butanolate.), (Dmamp) ₂ (In the formula, dmamp is 1-dimethylamino-2-methyl-2-propanol.), Bis (pentamethylcyclopentadienyl) (C ₅ (CH ₃ ). ) ₅ ) ₂ and carbonyl (CO) such as tetracarbonyl (CO) ₄ may be contained. Therefore, in some embodiments, the nickel-based precursor AX is, for example, nickel aminate (Ni (AMD)), nickel di (cyclopentadienyl) (Ni (Cp), to name a few. ) ₂ ), Nickel Di (Ethylcyclopentadienyl) (Ni (EtCp) ₂ ), Bis (2,2,6,6-Tetramethylheptane-3,5-Zionato) Ni ^(II) (Ni (thd) ₂ ), Nickel acetylacetonate (Ni (acac) ₂ ), bis (methylcyclopentadienyl) nickel (Ni (CH ₃ C ₅ H ₄ ) ₂ ), nickel dimethyl glyoxymate (Ni (dmg) ₂ ), nickel 2-Amino-penta-2-en-4-onato (Ni (apo) ₂ ), Ni (dmamb) ₂ (in the formula, dmamb = 1-dimethylamino-2-methyl-2-butanolate), Ni (dmamp) ₂ (In the formula, dmamp is 1-dimethylamino-2-methyl-2-propanol.), Bis (pentamethylcyclopentadienyl) nickel (Ni (C ₅ (CH ₃ ) ₅ ) ₂ ) and nickel. It may contain carbonyl (Ni (CO) ₄ ). In the formula (6a), the precursor "BY" includes oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), hydrogen peroxide (H ₂ O ₂ ) and the like, to name a few examples. May contain an oxidizing agent of. In other embodiments, plasma can be used with an oxidant to form oxygen radicals, as described further herein later.

However, in certain embodiments, dopants containing an electron-donating or back-donating positive material in addition to the precursors AX and BY can be utilized to form a layer of the CEM device. Further dopant ligands, including electron-donating or back-donating positive materials, can flow in parallel with the precursor AX, but donating or donating substantially according to equation (6b) below. It may allow the formation of back-donating compounds. In a plurality of embodiments, the dopant containing a donor or backdonant material such as ammonia (NH ₃ ), methane (CH ₄ ), carbon monoxide (CO) or other material is another arrangement containing carbon or nitrogen. Other dopants, including the donors or donor or backdonant materials listed above, can be utilized as well as available. Therefore, the formula (6a) is the following formula (6b).
AX _(gas) + (NH ₃ or other ligand containing nitrogen) + BY _(gas)
= AB: NH _{3 (solid)} + XY _(gas) (6b)
Can be modified to include additional dopant ligands, including donor or backdonant materials, substantially according to.

Concentrations such as atomic concentrations of precursors of formulas (6a) and (6b) such as AX, BY and NH ₃ (or other ligands containing nitrogen) are approximately 0.1% in the manufactured CEM device. The final nitrogen-based or carbon-based dopant molecule containing donor or reverse donor materials such as the form of ammonia (NH ₃ ) or carbonyl (CO), occupying a concentration between ~ 10.0%. It should be noted that it can be adjusted to provide a specific atomic concentration. However, the claimed subject matter is not necessarily limited to the precursors and / or atomic concentrations identified above. Conversely, the patented subjects are atomic layer deposition, chemical gas phase deposition, plasma chemical gas phase deposition, spatter deposition, physical gas phase deposition, hot wire chemical gas phase deposition, which are used in the manufacture of CEM devices. It is intended to include all such precursors used in laser-accelerated chemical vapor phase deposition, laser-accelerated atomic layer deposition, rapid heating chemical vapor phase deposition, spin-on deposition, and the like. In formulas (6a) and (6b), "BY" refers to oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), hydrogen peroxide (H ₂ O ₂ ), to name a few examples. ) And the like may be contained. In other embodiments, plasma can be used in conjunction with an oxidant (BY) to form oxygen radicals. Similarly, plasma may be used with a doping species containing a donor or backdonant material to form an activated species, thereby controlling the doping concentration of the CEM.

In certain embodiments, such as those utilizing atomic layer growth, the substrate is a dopant (ammonia, or) containing precursors such as AX and BY and electron-donating or back-donating positive materials in a heated chamber. It may be exposed to (eg, nickel-amides, nickel-imides, nickel-amidinates or other ligands containing metal-nitrogen bonds such as combinations thereof), and the chamber may be exposed to, for example, in certain embodiments. For example, temperatures in the range of approximately 20.0 ° C to 1000.0 ° C, or temperatures in the range of approximately 20.0 ° C to 500.0 ° C can be reached. For example, in one particular embodiment in which atomic layer growth of NiO: NH ₃ is performed, a chamber temperature range of approximately 20.0 ° C to 400.0 ° C can be utilized. In response to exposure to precursor gases (eg, AX, BY, NH ₃ or other ligands containing nitrogen), such gases last in the range of approximately 0.5 to 180.0 seconds. It can be purged from the heated chamber over a period of time. However, it should be noted that these are merely examples of possible ranges with respect to chamber temperature and / or time, and the claimed subject matter is not limited in this regard.

In certain embodiments, a cycle with one two precursors utilizing atomic layer growth (eg, AX and BY as described for formula 6 (a)) or one three precursors. Cycle with (eg, AX, NH ₃ , CH ₄ , or other ligands containing nitrogen, carbon, or other ligands containing electron-donating or back-donating materials, as described for formula 6 (b)). Dopants and BY) can result in a CEM device layer that occupies a thickness in the range of approximately 0.6 Å to 5.0 Å per cycle. Thus, in one embodiment, an atomic layer deposition process in which the layer occupies a thickness of approximately 0.6 Å is utilized to form a CEM device film occupying a thickness of approximately 500.0 Å, for example 800-900 times. Cycle may be utilized. In another embodiment, a cycle with two precursors, eg 100, utilizing an atomic layer deposition process in which the layer occupies approximately 5.0 Å. Atomic layer deposition may be utilized to form CEM device films with other thicknesses, such as thicknesses in the range of approximately 1.5 nm to 150.0 nm, and the claimed subject matter is in this regard. It should be noted that it is not limited.

In certain embodiments, a cycle with one or more precursors of atomic layer growth (eg, AX and BY) or a cycle with three precursors (AX, NH ₃ , CH ₄ , or nitrogen, carbon). In response to other ligands, including, or other dopants, including donor or backdonant materials, and BY), the CEM device film may allow improvement in film properties, or in the form of a carbonyl or ammonia. Dopants containing, such as electron donating or back donating positive materials, may undergo in situ annealing that can be used to incorporate into the CEM device film. In certain embodiments, the chamber may be heated to a temperature in the range of approximately 20.0 ° C to 1000.0 ° C. However, in other embodiments, in situ annealing may be performed utilizing a chamber temperature in the range of approximately 100.0 ° C to 800.0 ° C. In situ annealing time may be obtained over a duration ranging from approximately 1.0 second to 5.0 hours. In certain embodiments, the annealing time can be such that it falls within a narrower range, for example, from about 0.5 minutes to about 180.0 minutes, and the claimed subject matter is not limited in these respects. ..

In certain embodiments, a CEM device manufactured by the above method has a "born on property" in which the device exhibits a relatively low impedance (relatively high conductivity) immediately after the device is made. ) Can be shown. Thus, if the CEM device is integrated into a larger electronics environment, for example in the desired activation, the relatively low voltage applied to the CEM device will be CEM, as shown by region 104 in FIG. 1A. It can allow relatively high current flow through the device. For example, as described herein above, in at least one possible embodiment, for example, a V _reset can occur at a voltage in the range of approximately 0.1V to 1.0V and a V _set can be from 1.0V. It can occur at voltages in the range of 2.0V. Thus, for example, a storage circuit can write to, for example, a CERAM storage device, read from a CERAM storage device, or change the state of a CERAM switch with an electrical switching voltage operating in the range of approximately 2.0 V or less. In a plurality of embodiments, such relatively low voltage operation can reduce complexity and cost and may provide other advantages over competing memory and / or switching device technologies. can.

FIG. 2 is an explanatory diagram of an embodiment of a switching device including filaments in a transition metal oxide film formed between conductive materials. For example, the conductive substrate such as the conductive substrate 210 is made of titanium nitride (TiN) manufactured as a plurality of layers for the purpose of use in a device mainly composed of CEM of any other kind for use in a CERAM switching device, for example. ) And the like, which are mainly composed of titanium and / or may contain a titanium-containing substrate. In another embodiment, the conductive substrate 210 is a titanium nitride, platinum, titanium, copper, aluminum, cobalt, nickel, tungsten, tungsten nitride, cobalt silicate, ruthenium oxide, chromium, gold, palladium, indium tin oxide, Other types of conductive materials such as tantalum, silver, iridium or any combination thereof may be included. In another embodiment, the conductive substrate 210 is formed as multiple layers, such as tantalum nitride (TaN), for use in CERAM devices or in any other type of CEM-based device. The tantalum-based material and / or the tantalum-containing material may be included, and the claimed subject matter is not limited in this respect. In a plurality of embodiments, the TaN substrate can be formed utilizing a precursor such as, for example, pentakisdimethylamide tantalum (PDMAT).

In another embodiment, the conductive substrate 210 comprises tungsten, such as tungsten nitride (WN), formed as a plurality of layers for use in, for example, CERAM devices or other types of CEM-based devices. It may contain a main material and / or a tungsten-containing material. In multiple embodiments, the WN substrate can be formed utilizing precursors such as, for example, Tungsten Hexacarbonyl (W (CO) ₆ ) and / or Cyclopentadienyl Tungsten (II) Tricarbonyl Hydride. In another embodiment, the WN substrate is, for example, triamine tungstentricarbonyl ((NH ₃ ) ₃ W (CO) ₃ ) and / or tungsten pentacarbonylmethylbutylisonitrile (W (CO) ₅ (C ₅ H ₁₁ NC)). ) Can be formed. The conductive overlay 240 may contain, for example, one or more materials similar to the materials constituting the conductive substrate 210, or may contain completely different materials, and the claimed subject matter. Is not limited in this regard.

In certain embodiments, the filament 230 may form between the conductive substrate 210 and the conductive overlay 240 in response to the application of a voltage within a particular range. In certain embodiments, the filament may correspond to a low resistance crystalline path between the conductive substrate 210 and the conductive overlay 240. As mentioned above, filament formation may include, for example, a redox reaction by one or more nanoionics that can result in an oxidized state of the transition metal oxide film. In other embodiments, filament formation can be brought about by ion transport utilizing an empty lattice point-ion diffusion process.

However, by forming the filament 230 in the transition metal oxide film 220, the device can perform a switching operation in response to an application of a voltage level, eg, in the range of approximately 3.0 V or less, but by filament formation. Switching devices can be disabled or interfered with in response to quantum mechanically correlated electronic phenomena. For example, filament formation can allow the accumulation of parasitic charges in devices constructed from transition metal oxide films, which can increase the capacitance of parasitic devices. Therefore, as the parasitic capacitance increases, the operation of the CEM device at high frequencies may be impaired.

Thus, in certain embodiments, the formation of conductive filaments is reduced or reduced to allow a low impedance, low capacitance path for the current flowing between the conductive substrate 210 and the conductive overlay 240. It can be advantageous to eliminate. By avoiding filament formation, for example in a CEM device formed from a transition metal oxide, the "innate" properties of the CEM device can also be preserved, and the "innate" properties are relative in response to device fabrication. Refers to the ability of a CEM device to exhibit relatively low impedance (relatively high conductivity).

3A-3D are explanatory views illustrating electron donation and back donation via sigma and pi bonds of a metal-carbonyl molecule in a CEM according to one embodiment. As described above, a change in the impedance state of a CEM device, such as a change from a low impedance state to a high impedance state, causes donation or back donation of electrons starting from a metal atom such as a ligand and Ni. Can be brought about by. In certain embodiments as described with respect to FIGS. 3A-3D, electron donations that occur in a first direction, such as from a ligand molecule to a metal atom, occur, for example, in a CEM containing NiO: CO. It can be achieved by sigma bonds, which may contain the higher (or highest) occupied molecular orbitals of the carbonyl ligand. Electron backbonding that occurs in a second direction, such as from a metal atom to a ligand molecule, can be achieved by a π bond, which may correspond, for example, to the lowest empty molecular orbital of the carbonyl ligand.

To illustrate electron donation or back donation, embodiment 300 (FIG. 3A) serves, for example, as a substituted ligand for a CEM such as a CEM containing nickel oxide (NiO), at least in certain embodiments. NiO: Represents a carbonyl (CO) molecule capable of forming CO. In the embodiment of FIG. 3A, the sigma bond 310 allows one or more electrons to move from the CO ligand towards the metal ion of the CEM, eg NiO, the binding electron. Can represent an orbit. In embodiment 320 (FIG. 3B), the π-bonding 322 and 324 include, for example, a semi-bonding orbital representing the lowest empty molecular orbital of a CO ligand. In certain cases with respect to CO ligands, the π bonds 322 and 324 can accept electrons from the "d" orbital of a metal atom such as Ni. In certain cases, the electron back-donating material is a carbonyl (CO), nitrosyl (NO), isocyanide (RNC. In the formula, R is H, C _1-1 to C ₆ alkyl or C ₆ to C ₁₀ aryl. ), Alkene (eg, ethene), alkyne (eg, _ethine ) or trialkylphosphine or triarylphosphine ( _R3P . _In the _formula , R is C1 to C6 alkyl or C6 to _C10aryl . ) Etc., π back-bonding ligand.

In embodiment 340 (FIG. 3C), metal atoms that may contain Ni, for example in a CEM containing NiO: CO, are shown as accepting electrons from the sigma bond of the carbonyl ligand. In one embodiment, the electrons received from the sigma bond of the carbonyl ligand can, for example, supplement the "d" orbital of the Ni atom, which causes the atom to be in a 2+ oxidized state (eg, Ni ²⁺ in a material). It can be changed to NiO: CO or NiO: NH ₃ etc.). Therefore, the electron donation for transitioning the CEM device to a relatively conductive state is given by the following equation (7).
Ni ¹⁺ + Ni ³⁺ → 2Ni ²⁺ (7)
Can be summarized substantially according to.

In embodiment 360 (FIG. 3D), metal atoms that may contain Ni, for example in a CEM containing NiO: CO, are the "d" orbitals 335 and the Ni atom (represented by M in FIGS. 3C and 3D). Electrons are back-donated from 337 and are shown as reversing the back-donation process. In certain cases with respect to the NiO: CO complex, as shown in FIG. 3D, electrons from the "d" orbital are donated to the lower (or lowest) empty molecular orbital (π bond) of the CO molecule. As described herein with respect to equation (4), backbonding can cause disproportionation, which is (same as equation (4)) equation (8).
2Ni ²⁺ → Ni ¹⁺ + Ni ³⁺ (8)
May include simultaneous oxidation and reduction according substantially to.

In the above case, such disproportionation can result in, for example, a relatively high impedance state during operation of the CEM device, of the nickel ions as Ni ¹⁺ + Ni ³⁺ represented by equation (8). Refers to formation.

FIG. 3E shows a representative NiO complex 380 containing a defect in the form of oxygen empty lattice points in a correlated electronic material according to one embodiment that can be supplemented by the carbonyl molecules of FIGS. 3A-3D. In certain embodiments, the NiO complex 385 may represent the coordination sphere of Ni atoms 390 and 391. As mentioned above, such defects that may include oxygen empty lattice points 395 can cause degradation of electron donation and back donation in the CEM material. Deterioration of electron donation and back donation in the CEM material, in turn, reduces the conductivity of the CEM-based device and increases the electrified storage in the CEM-based device, which increases the parasitic capacitance. , This can result in reduced high frequency switching performance) and / or affect other performance aspects of CEM-based devices, but the claimed subject matter is not limited in this regard. ..

Thus, in the embodiment of FIG. 3E, a defect in the NiO complex 385, such as, for example, oxygen empty lattice point 395, can act as a substituted ligand capable of filling the oxygen empty lattice point 395, CO ligand 397 or NH. It can be supplemented by ₃ ligands 398. The CO ligand 397 or NH ₃ ligand 398, for example, a CEM film containing NiO exposed to gaseous CO (or gaseous NH ₃ ) in a chamber, eg, at a temperature in the range of approximately 100 ° C to 800 ° C. It can be introduced into the CEM film by utilizing the annealing process. In certain embodiments, substituted ligands such as, for example, CO ligand 397 and NH ₃ ligand 398, can act to regulate the local electrical negativeness of the coordination sphere, thereby It can promote electron donation or back donation. Thus, the presence of substituted ligands such as, for example, CO ligand 397 and NH ₃ ligand 398, can act to reduce the concentration of defects in the coordination sphere forming the CEM. In multiple embodiments, by facilitating electron donation or back donation, by reducing the concentration of defects in the coordination sphere forming the CEM, the conductivity is increased, the capacitance is reduced, and / or the CEM is predominant. It is possible to bring about further performance improvement of the device. Furthermore, the promotion of electron donation or back donation may inhibit the formation of filaments by nanoionics, which may form conductive filaments in the transition metal oxide film, and may not occur.

4A and 4B are graphs illustrating the energy relative to the density of states in a nickel-based CEM according to one embodiment containing oxygen as the dominant ligand. In embodiment 400 (FIG. 4A), the vacant conduction band 410, sometimes referred to as the upper Hubbard band, is located just above the Fermi level. The valence band 420, sometimes referred to as the lower Hubbard band, is slightly below the Fermi level. For example, the energy graph relative to the density of states in FIG. 4A, which indicates that electrons can move relatively easily between the conduction band and the valence band of the CEM, is in the conductive state (eg, the metallic state). Corresponds to a working CEM. In a particular example, the energy graph relative to the density of states in FIG. 4A may correspond to a low impedance (conductive) state where electron donation or back donation is frequent. Examples of Ni-containing CEM-based materials such as NiO that utilize carbonyl and / or ammonia as substituted ligands (NiO: CO and NiO: NH ₃ ) are compared to the state densities in FIG. 4A. The energy graph can indicate the condition that the "3d" orbital of the Ni atom contains 8 electrons and Ni contains a 2+ oxidation number. This relationship is related to the following equation (9).
2Ni ²⁺ => 3d ⁸ + 3d ⁸ (9)
Can be summarized in.

Further, in certain embodiments, NiO can operate as a P-type CEM device that can act to push the Fermi level downwards, such as in the direction of the valence band 420, in FIG. 4A. In this regard, the "P-type doped CEM" referred to herein comprises a particular molecular dopant that exhibits increased conductivity compared to a non-doped CEM when the CEM operates at low impedance. , Means the first type of CEM. The introduction of substituted ligands such as CO and NH ₃ can work to improve the P-type properties of NiO-type CEMs. Therefore, at least in certain embodiments, one attribute of the P-type operation of the CEM is the ability to adjust or individually modify the conductivity of the CEM operating at low impedance by controlling the atomic concentration of the P-type dopant in the CEM. May include. In certain embodiments, increasing the atomic concentration of the P-type dopant can increase the conductivity of the CEM, but the claimed subject matter is not limited in this regard.

In embodiment 450 (FIG. 4B), the band splitting potential (U), which can represent the difference between ionization energy and electron affinity in a particular embodiment, separates the conduction band 460 from the valence band 470. Therefore, the energy graph relative to the density of states in FIG. 4B indicates that the electrons can be restricted so that they do not operate between the conduction band and the valence band of the CEM. ) Corresponds to the CEM that can operate in the state. An example of a CEM-based material containing Ni, such as NiO, which utilizes carbonyl and / or ammonia as a substituted ligand (NiO: CO and NiO: NH ₃ ), is compared to the state density in FIG. 4A. The energy graph can indicate the condition that the first "3d" orbital of the Ni atom contains 7 electrons, while the second "3d" orbital of Ni contains 9 electrons. .. In this example, the oxidation numbers of adjacent Ni atoms in the coordination sphere, such as the NiO complex 385 in FIG. 3E, may be non-uniform with respect to each other, such as Ni ¹⁺ and Ni ³⁺ , where Ni is the oxidation number of 2+. May include. This relationship is related to the following equation (10).
Ni ¹⁺ + Ni ³⁺ => 3d ⁷ + 3d ⁹ (10)
Can be summarized in.

FIG. 5 is a flow chart of Embodiment 500 of the method for manufacturing correlated electronic materials. Exemplary implementations as described in FIG. 5 and the other drawings described herein occur in a different order than those presented and described, blocks other than those presented and described, fewer blocks, or those that may be identified. Blocks, or any combination thereof may be included. The method of FIG. 5 may be initiated in block 510, which may include the step of forming one or more layers of CEM on the substrate in the chamber. One or more layers of CEM can be formed from transition metals and dominant ligands. One or more layers of the CEM may have concentration defects in the coordination sphere that form the CEM. The method of FIG. 5 may remain in block 520, which comprises exposing one or more layers of the CEM to a molecular dopant containing a substituted ligand to form a P-type CEM. You may be. Substituted ligands can act to concentrate the defects in the coordination sphere that form the CEM, but reducing the concentration of defects in the coordination sphere is in one or more layers of the CEM. Inhibits the formation of conductive filaments.

As described above in the present specification, a molecular dopant such as carbonyl (CO) causes a disproportionation reaction of the formula (4) and a reversal of the disproportionation reaction of the formula (4) substantially according to the formula (5). As such, it may enable electron sharing during operation of the CEM device. Therefore, when carbonyl is used as the molecular dopant, FIG. 6A is a flow chart of a method for making a correlated electronic device material according to one embodiment 601. Illustrative implementations, such as those described in FIGS. 6A, 6B and 6C, are blocks other than those presented and described, fewer blocks, or blocks that occur in a different order than can be identified. Alternatively, any combination thereof may be included. In one embodiment, the method may include, for example, blocks 610, 630 and 650. The method of FIG. 6A may follow the schematic description of atomic layer deposition described above herein. The method of FIG. 6A may be initiated in block 610, wherein the block 610 exposes the substrate to, for example, a first precursor in a gaseous state (eg, "AX") in a heated chamber. The first precursor may include a transition metal oxide, a transition metal, a transition metal compound or any combination thereof and a first ligand. In one example, as described in block 610, nickel cyclopentadienyl (Ni (Cp) ₂ ) may be utilized, where Ni represents the transition metal and Cp represents the cyclopentadienyl configuration. Represents a rank. The method may remain in block 620, which may include the step of removing precursors AX and by-products of AX by the use of inert gas or exhaust or a combination thereof. The method may remain in block 630, which may include the step of exposing the substrate to a second precursor in gaseous state (eg, BY), where the second precursor is. It contains oxides to form the first layer of film for CEM devices. The method may remain in block 640, which may include the step of removing the precursor BY and by-products of BY by the use of an inert gas or exhaust or combination. The method may remain in block 650, which allows the correlated electronic material to show the ratio of the first impedance state to the second impedance state, which is at least 5.0: 1.0. It comprises repeating the steps of exposing the substrate to the first and second precursors using an intermediate purge and / or exhaust step that forms an additional layer of film until possible. May be good.

FIG. 6B is a flow chart of a method for manufacturing a correlated electronic device material according to the embodiment 602. The method of FIG. 6B may follow a schematic description of a modified form of CVD such as chemical vapor deposition or CVD or plasma accelerated CVD. In FIG. 6B, in block 660 and the like, the substrate may be simultaneously exposed to the precursors AX and BY under pressure and temperature conditions that promote the formation of AB corresponding to CEM. Using further techniques such as applying DC plasma or remote plasma, using hot wires to partially decompose precursors, or lasers to accelerate reactions, which is an example of the form of CVD, CEM May result in the formation of. The CVD film process and / or modified form is electrical, for example, the ratio of the first impedance state to the second impedance state, where the correlated electron material has the appropriate thickness and is at least 5.0: 1.0. It can be obtained over a period of time under conditions determinable by one of ordinary skill in CVD until it exhibits suitable properties, such as properties.

FIG. 6C is a flow chart of a method for manufacturing a correlated electronic device material according to the embodiment 603. The method of FIG. 6C may follow a schematic description of physical vapor deposition or PVD or sputtered vapor deposition or modifications of these methods and / or related methods. In FIG. 6C, in block 671, the substrate is an impact flow of precursor having a "line of sight" in the chamber, for example, under certain conditions of temperature and pressure that facilitates the formation of a CEM containing material AB. May be exposed to. The source of the precursor may be, for example, AB or A and B from separate "targets", and the deposit is composed of material A or B or AB, either physically or thermally or by other means. It is taken from a target (sputtered) and achieved using the flow of atoms or molecules contained in the "line of sight" of the substrate. In one implementation, a process chamber may be utilized and the pressure in the process chamber approximates a lower threshold or a pressure value below the threshold, resulting in an atom or molecule or the mean free path of A or B or AB. Includes sufficiently low values, such as pressure values that are approximately the distance from the target to the substrate or longer than this distance. AB (or A or B) or both flows so as to form AB on the substrate under conditions of reaction chamber pressure, substrate temperature and other properties controlled by those skilled in the art of PVD and sputter deposition. Can be together. In other embodiments of PVD or sputter deposition, the ambient environment may be a source such as BY, or to form, for example, carbon or CO, eg, co-sputtered carbon-doped NiO. Peripheral O ₂ may be used for the purpose of reacting the sputtered nickel. The PVD film and the modified form of the PVD film are deposited with a thickness and characteristic correlated electronic material that can show the ratio of the first impedance state to the second impedance state, which is at least 5.0: 1.0. Until, under conditions determinable by those skilled in the art of PVD, it may continue for the required time.

This method may remain in block 672, and in at least some embodiments, metals such as nickel can be sputtered from the target and transition metal oxides can be formed in subsequent oxidation processes. This method may remain in block 673, and in at least some embodiments, the metal or metal oxide is in a chamber containing gaseous carbon with or without a significant portion of oxygen. Can be sputtered.

As mentioned above for block 610 in FIG. 6A, Ni (Cp) ₂ is pointed to as a possible example of transition metals and ligands used in the formation of CEM films. Thus, FIG. 7 shows a bis (cyclopentadienyl) molecule (Ni (C ₅ H ₅ ) ₂ ) that can serve as an exemplary precursor of the gaseous form utilized in the fabrication of correlated electronic material devices according to one embodiment. ) Is provided. In a plurality of embodiments, Ni (C ₅ H ₅ ) ₂ can function as a precursor in the gaseous form utilized in the fabrication of correlated electronic materials according to one embodiment 700. As shown in FIG. 7, the nickel atom near the center of the nickel di (cyclopentadienyl) molecule is transformed into a +2 ionized state to form Ni ²⁺ ions. In the exemplary molecule of FIG. 7, additional electrons are present at the upper left and lower right CH ^- sites in the cyclopentadienyl (Cp) portion of the nickel di (cyclopentadienyl) (Ni (Cp) ₂ ) molecule. do. FIG. 7 further illustrates the abbreviation showing nickel bound to two pentagonal cyclopentadienyl ligands.

8A-8D show the sub-processes used in the method for making NiO-based films containing CEM according to one embodiment. The subprocesses of FIGS. 8A-8D may correspond to an atomic layer deposition process for depositing the components of NiO: CO on a conductive substrate using the precursors AX and BY of formula (6). .. In a plurality of embodiments, the conductive substrate may include an electrode material containing materials similar to those utilized in the construction of the conductive substrate 210, as described herein with respect to FIG. good. However, with appropriate material replacement, the subprocesses of FIGS. 8A-8D are used to make films containing other transition metals, transition metal oxides, transition metal compounds or CEMs utilizing combinations thereof. Often, the subject matter claimed is not limited in this regard.

As shown in FIG. 8A (Embodiment 800), the substrate, such as substrate 850, has a duration ranging from approximately 0.5 seconds to 180.0 seconds to nickel di (cyclopentadienyl) (Ni). (Cp) It is possible to expose to a first gaseous precursor such as the precursor AX of the formula (6a) such as a gaseous precursor containing ₂ ). As mentioned above, the concentration and exposure time of the first gaseous precursor, such as atomic concentration, is such that the final atomic concentration of carbon, such as in the form of carbonyl, is, for example, approximately 0.1% in the finished material. It can be adjusted to be between ~ 10.0%. As shown in FIG. 8A, exposure of the substrate to gaseous Ni (Cp) ₂ results in the attachment of _two Ni (Cp) molecules or Ni (Cp) motifs at various locations on the surface of the substrate 850. Can be caused. Sedimentation can be carried out in a heated chamber, for example, which can reach temperatures in the range of approximately 20.0 ° C to 400.0 ° C. However, it should be noted that further temperature ranges are possible, such as temperature ranges below approximately 20.0 ° C and above approximately 400.0 ° C, and the claimed subject matter is not limited in this regard.

As shown in FIG. 8B (Embodiment 810), after exposing a conductive substrate such as a conductive substrate 850 to a gaseous precursor such as a gaseous precursor containing Ni (Cp) ₂ , the chamber Can purge residual gaseous Ni (Cp) ₂ and / or Cp ligands. In one embodiment, for an example of a gaseous precursor containing Ni (Cp) ₂ , the chamber can be purged for a duration ranging from approximately 0.5 seconds to 180.0 seconds. In one or more embodiments, the purge duration is, for example, present in unreacted ligands and by-products and transition metals, transition metal compounds, transition metal oxides or similar surfaces and process chambers. It may depend on the affinity of the surface (excluding chemical bonds). Therefore, for the example of FIG. 8B, if the unreacted Ni (Cp) ₂ , Ni (Cp), Ni and other by-products show increased affinity for the substrate or chamber surface, it is long. The purge duration may be utilized to remove residual gaseous ligands such as those mentioned. In other embodiments, the purge duration may depend, for example, on the gas flow in the chamber. For example, a gas flow in a chamber where laminar flow is dominant can remove residual gaseous ligands at a faster rate, while a gas flow in a chamber where turbulence is dominant is slower. The residual ligand can be removed at the same rate. It should be noted that the claimed subject matter is intended to include purging residual gaseous material, regardless of the flow characteristics within the chamber.

As shown in FIG. 8C (Embodiment 820), a second gaseous precursor, such as the precursor BY of formula (6a), can be introduced into the chamber. As mentioned above, the second gaseous precursor may contain an oxidant, which dispels the first ligand, such as Cp, to give some examples oxygen (O). ₂ ) It can act to replace the ligand with an oxidant such as ozone (O ₃ ), nitrogen monoxide (NO), hydrogen peroxide (H ₂ O ₂ ). Therefore, as shown in FIG. 8C, the oxygen atom can form a bond with at least some nickel atoms bonded to the substrate 850. In one embodiment, the precursor BY is the following formula (11).
Ni (C ₅ H ₅ ) ₂ + O ₃ → NiO +
Possible by-products (eg CO, CO ₂ , C ₅ H ₅ , C ₅ H ₆ , CH ₃ , CH ₄ , C ₂ H ₅ , C ₂ H _{6, ...} ) (11)
(In this case, C ₅ H ₅ replaced Cp in formula (11)) to oxidize Ni (Cp) ₂ to form some additional oxidants and / or combinations thereof. be able to. As shown in FIG. 8C, some possible by-products are shown, including C ₂ H ₅ , CO ₂ , CH ₄ and C ₅ H ₆ . Similarly, as shown in FIG. 8C, the carbonyl (CO) molecule can bind to the nickel oxide complex, eg, at sites 860 and 861 and the like. In multiple embodiments, such nickel-carbonyl and bond (eg, NiO: CO) is a substantially rapid conductor / of the CEM device, eg, at atomic concentrations between 0.1% and 10.0%. Insulator transitions can be brought about.

Possible, for example, CO, CO ₂ , C ₅ H ₅ , C ₅ H ₆ , CH ₃ , CH ₄ , C ₂ H ₅ , C ₂ H ₆ , etc., as shown in FIG. 8D (Embodiment 830). Hydrocarbon by-products can be purged from the chamber. In certain embodiments, such chamber purging is performed with a pressure ranging from approximately 0.01 Pa to 105.0 kPa over a duration ranging from approximately 0.5 seconds to 180.0 seconds. Can be done.

In certain embodiments, the described subprocesses presented in FIGS. 8A-8D can be repeated until a desired thickness, such as a thickness in the range of approximately 1.5 nm to 100.0 nm, is achieved. As described above herein, atomic layer deposition methods such as those presented and described with reference to FIGS. 8A-8D are, for example, approximately 0.6 Å to 1.5 Å for a single ALD cycle. A CEM device film having a thickness in the range of can be produced. Therefore, in order to construct a CEM device film that occupies a thickness of 500.0 Å (50.0 nm), as a simple example, about 300 to 900 cycles with two precursors using AX + BY, for example, are performed. It may be carried out. In certain embodiments, the cycle may sometimes interrupt between different transition metals and / or transition metal compounds and / or transition metal oxides in order to obtain the desired properties. For example, in one embodiment, two atomic layer deposition cycles in which a NiO: CO layer can be formed are followed by, for example, three atomic layer deposition cycles for forming a titanium oxide carbonyl complex (TIO: CO). You may. Other interruptions of transition metals and / or transition metal compounds and / or transition metal oxides are also possible, and the claimed subject matter is not limited in this regard.

In certain embodiments, after the completion of one or more atomic layer deposition cycles, the substrate can be annealed, thereby assisting in controlling the grain structure, densifying the CEM film, or film properties. Performance or durability can be improved. For example, if atomic layer deposition yields a number of columnar grains, annealing allows the boundaries of the columnar grains to be deposited together, which boundaries, for example, reduce changes in resistance of CEM devices, for example. be able to. Annealing can provide additional benefits, such as more uniform distribution of carbon molecules such as carbonyls throughout the CEM device material, and the claimed subject matter is not limited in this regard.

9A-9D are diagrams showing the time-dependent precursor flow rate and temperature profile that can be used in the method for making CEM devices such as NiO-based devices according to one embodiment. For FIGS. 9A to 9D, a common time scale (T ₀ to T ₈ ) is used. FIG. 9A shows a precursor gas flow profile 910 for a precursor (eg, AX) according to embodiment 901. As shown in FIG. 9B, the precursor gas flow rate may be increased to allow the precursor gas to enter the chamber in which the CEM device is made. Therefore, according to the precursor gas flow rate profile 910, at time _T0 , the gas flow rate of the precursor AX may be approximately 0.0 (eg, a negligible amount). _At time T1, the gas flow rate of precursor AX may be increased to a relatively higher value. _At time T2, which can be accommodated after _a time ranging from time T1 to approximately 0.5 to 180.0 seconds, the precursor AX gas may be purged and / or exhausted from the chamber, for example by purging or the like. can. The precursor AX gas flow rate can be stopped until approximately time _T5 , at which time the precursor _AX gas flow rate can increase to a relatively higher value. After time _T5 , such as at time _T6 and _T7 , the precursor AX gas flow rate may be returned to 0.0 (eg, a negligible amount) until increased at a later point in time.

FIG. 9B shows the gas flow rate profile 920 of the purge gas according to one embodiment 902. As presented in FIG. 9B, the purge gas flow rate can be increased or decreased to allow, for example, the exhaust of precursor gases AX and BY from the production chamber. At time T ₀ , the purge gas profile 920 points to a relatively high purge gas flow rate, which allows the impurity gas in the production chamber to be removed prior to time T ₁ . _At time T1, the purge gas flow rate may be returned to approximately 0.0, which allows the introduction of precursor AX gas into the production chamber. _At time T2, the purge gas flow rate increased over a duration ranging from approximately 0.5 seconds to 180.0 seconds to allow removal of excess precursor gas AY and reaction by-products from the production chamber. You may let me.

FIG. 9C shows a gas flow rate profile 930 of a precursor gas (eg, BY) according to one embodiment 903. As presented in FIG. 9C, the gas flow rate of the precursor BY can remain at a flow rate of approximately 0.0 until approximately time T3 _, where the gas flow rate is increased to a relatively higher value. You may. At a time T ₄ , which may correspond after a time in the range of approximately 0.5 seconds to 180.0 seconds from the time T ₂ , the precursor BY gas may be purged and / or exhausted from the chamber, for example by purging or the like. can. The gas flow rate of the precursor BY may be returned to 0.0 until _{approximately} time _T7 , at which time the gas flow rate of the precursor BY is increased to a relatively higher value. May be good.

At time T3 _, the purge gas flow rate may be reduced to a relatively low value, which allows the precursor BY gas to enter the production chamber. After exposure of the substrate to the precursor BY gas, the purge gas flow rate may also be increased to allow removal of the precursor BY gas from the fabrication chamber, for example a single CEM device film. It is possible to notify the completion of the atomic layer. After removal of the precursor BY gas, the precursor AX gas may be reintroduced into the fabrication chamber to initiate the deposition cycle of the second atomic layer of the CEM device film. In certain embodiments, the processes relating to the introduction of precursor AX gas into the fabrication chamber, the purging of residual precursor AX gas from the fabrication chamber, the introduction of precursor BY gas and the purging of residual precursor BY gas are eg, for example. It may be repeated in the range of about 300 to 900 times. Repeating the above process can result in, for example, a CEM device film having a thickness dimension between approximately 20.0 nm and 100.0 nm.

FIG. 9D is a diagram showing a time-dependent temperature profile used in the method for making correlated electronic device materials according to one embodiment 904. In FIG. 9D, the deposition temperature can be increased, for example, to reach a temperature in the range of approximately 20.0 ° C to 900.0 ° C. However, in certain embodiments, some narrower ranges may be utilized, such as a temperature range in the range of approximately 100.0 ° C to 800.0 ° C. Further, for certain materials, a narrower temperature range may be utilized, such as from about 100.0 ° C to about 600.0 ° C.

9E-9H are diagrams showing time-dependent precursor flow rates and temperature profiles that can be used in the method for making correlated electronic device materials according to one embodiment. For FIGS. 9E to 9H, a common time scale (T ₀ to T ₃ ) is used. As shown in 905, the precursor AX can be brought into the production chamber at time _T1 , where time _T0 to time _T1 is the purge gas flow rate as shown in embodiment 950. Used to purge and / or evacuate the process chamber in preparation for deposition. Embodiment 940 shows _a relative increase in the flow rate of precursor AX that occurs at time T1. Similarly, at time T1, the flow rate of the precursor BY, which is the _second reactant, can be increased as the gas flow rate increases at 960, as shown in embodiment 907. The two precursors (AX and BY) can flow substantially simultaneously for the amount of time required for the thickness of the CEM film. The temperature profile presented in FIG. 9H (Embodiment 908) shows that the temperature is set before or near time _T0 for deposition.

10A-10C are diagrams showing time-dependent temperature profiles used in the deposition and annealing process for making CEM devices according to one embodiment. As shown in FIG. 10A (Embodiment 1000), deposition can be carried out during an initial time frame such as T ₀ to T _{1 m} , during which time the CEM device film is an atomic layer. A deposition process can be utilized to deposit on a suitable substrate. An annealing period may follow after deposition of the CEM device film. In some embodiments, some atomic layer deposition cycles can range from, for example, approximately 10 cycles to 1000 or more cycles, but the claimed subject matter is not limited in this regard. After the completion of deposition of the CEM film on a suitable substrate, annealing at a temperature relatively higher than the deposition temperature or at the same or lower temperature is approximately 20.0 ° C. at time _T1n to time _{T1z and} the like. It can be carried out using a temperature in the range of (T _low ) to 900.0 ° C (T _high ). However, in certain embodiments, a narrower range, such as a temperature range in the range of approximately 100.0 ° C. (T _low ) to 800.0 ° C. (T _high ), may be utilized. Further, for certain materials, a narrower temperature range, such as about 200.0 ° C. (T _low ) to about 600.0 ° C. (T _high ), may be utilized. The annealing time can range from about 1.0 second to about 5.0 hours, but can also be narrowed, for example, with a duration of about 0.5 minutes to 180.0 minutes. It should be noted that the claimed subject matter is not limited to any particular temperature range for annealing the CEM device, and the claimed subject matter is not limited to any particular annealing duration. be. In other embodiments, the deposition method includes chemical vapor deposition, physical vapor deposition, sputtering, plasma accelerated chemical vapor deposition, other deposition methods for forming CEM films, or a combination of ALD and CVD, and the like. It may be a combination of deposition methods.

In a plurality of embodiments, annealing is gaseous nitrogen (N ₂ ), hydrogen (H ₂ ), oxygen (O ₂ ), water or water vapor (H ₂ O), nitrogen monoxide (NO), nitrogen sulfite (NO). N ₂ O), nitrogen dioxide (NO ₂ ), ozone (O ₃ ), argon (Ar), helium (He), ammonia (NH ₃ ), carbon monoxide (CO), methane (CH ₄ ), acetylene (C) ₂ H ₂ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), ethylene (C ₂ H ₄ ), butane (C ₄ H ₁₀ ) or any combination thereof. It can be carried out in a gaseous environment containing. Annealing can also be performed in a reduced pressure environment or at pressures up to and above atmospheric pressure, including pressures in multiple atmospheres.

As shown in FIG. 10B (Embodiment 1001), deposition can be carried out during an initial time frame such as T ₀ to T _{2 m} (deposition-1), and during this initial time frame, approximately 10 Atomic layer deposition cycles of up to approximately 500 times can be performed. At time T _2n , the annealing period can be initiated and continued until time T _2z . After time T _2z , the second set of atomic layer deposition cycles may be performed, perhaps as a number of cycles between approximately 10 and approximately 500 times. As shown in FIG. 10B, a second set of atomic layer deposition (deposition-2) cycles may be performed. In other embodiments, the deposition method includes chemical vapor deposition, physical vapor deposition, sputtering, plasma accelerated chemical vapor deposition, other deposition methods for forming CEM films, or a combination of ALD and CVD, and the like. It may be a combination of deposition methods.

As presented in FIG. 10C (Embodiment 1002), deposition can be carried out during an initial time frame such as time T ₀ to time T _{3 m} , and during this initial time frame approximately 10 to approximately 500 times. Atomic layer deposition cycles between can be carried out. At time T _3n , the first annealing period (annealing -1) can be initiated and continued until time T _3z . At time T _3j , the second set of atomic layer deposition cycles (deposition-2) can be carried out until time T _3k , at _which time the chamber temperature is the second annealing period (annealing). -2) can be increased, for example, in a manner that occurs to start at time T _{3 liters} . In other embodiments, the deposition method includes chemical vapor deposition, physical vapor deposition, sputtering, plasma accelerated chemical vapor deposition, other deposition methods for forming CEM films, or a combination of ALD and CVD, and the like. It may be a combination of deposition methods.

As described above herein, nitrogen-containing molecules (eg, ammonia, cyano (CN-), azide ion ( _N3- ⁾ , ^{ethylenediamine} _{( C2H8N2} ) and phen (1,10 _- phenanthroline)). Etc.), etc., the molecular dopants of the electrons during the operation of the CEM device so as to cause the disproportionation reaction of the formula (4) and the reversal of the disproportionation reaction of the formula (4) substantially according to the formula (5). May enable sharing. 11A-11C are flow charts of a method for making correlated electronic material films using nitrogen-containing molecules according to one or more embodiments. Exemplary implementations, such as those described in FIGS. 11A, 11B and 11C, are blocks other than those presented and described, fewer blocks, or blocks that occur in a different order than can be identified. Alternatively, any combination thereof may be included. In one embodiment, the method may include, for example, blocks 1110, 1120, 1130, 1140 and 1150. The method of FIG. 11A (Embodiment 1101) may follow the schematic description of atomic layer growth described above herein. The method of FIG. 11A may be initiated in block 1110, which comprises the step of exposing to, for example, a first precursor in a gaseous state (eg, "AX") in a heated chamber. The first precursor may be a transition metal oxide, a transition metal, a transition metal compound or any combination thereof and a first ligand (the first ligand needs to include a nitrogen dopant source). Does not include). Examples of nitrogen-containing ligands for nickel precursors include nickel-amides, nickel-imides and nickel-amidinates (Ni (AMD)). The method of FIG. 11A may remain in block 1120, which may include the step of removing excess precursor AX and by-products of AX by inert gas or exhaust or a combination thereof. The method of FIG. 11A may remain in block 1130, which may include the step of exposing the substrate to a second precursor in gaseous state (eg BY), the second precursor. Contains oxides to form the first layer of film of the CEM device and / or nitrogen-based precursors (ammonia (NH ₃ ), ethylene diamine (C ₂ H ₈ N ₂ ) or oxidation. Nitrogen series (N _x O _y components, etc.), such as nitric oxide (NO), nitrous oxide (N ₂ O), nitrogen dioxide (NO ₂ ), or precursors with NO ₃ ^- ligands, etc.) It may be contained. The method of FIG. 11A may remain in the block 1140, which is either by the use of the inert gas or by the exhaust, or by the combination of the exhaust of the process chamber and the purging of the process chamber with the inert gas. It may include the step of removing the excess precursor BY and by-products of BY. The method of FIG. 11A may remain in block 1150, where block 1150 indicates the ratio of the first impedance state to the second impedance state in which the correlated electron material is at least 5.0: 1.0. It comprises repeating the steps of exposing the substrate to the first and second precursors using an intermediate purge and / or exhaust step that forms an additional layer of film until possible. You may.

FIG. 11B is a flow chart of a method for making a correlated electronic device material using nitrogen-containing molecules according to one embodiment 1102. The method of FIG. 11B may follow a schematic description of a modified form of CVD such as chemical vapor deposition or CVD or plasma accelerated CVD. In FIG. 11B, in block 1160 and the like, the substrate may be simultaneously exposed to the precursors AX and BY under pressure and temperature conditions that promote the formation of AB corresponding to CEM. CEM using additional techniques such as application of DC plasma or remote plasma, use of hot wires to partially decompose precursors, or lasers to accelerate reactions, which is an example of the form of CVD. May result in the formation of. The CVD film process and / or modified form is electrical, for example, the ratio of the first impedance state to the second impedance state, where the correlated electron material has the appropriate thickness and is at least 5.0: 1.0. It can be carried out over a period of time under conditions determinable by one of ordinary skill in CVD until it exhibits suitable properties such as properties.

FIG. 11C is a flow chart of a method for making a correlated electronic device material using nitrogen-containing molecules according to one embodiment 1103. The method of FIG. 11C may follow a schematic description of physical vapor deposition or PVD or sputtered vapor deposition or modifications thereof and / or related methods. In FIG. 11C, the substrate is exposed in a chamber to a collision stream of precursor having a "line of sight" under certain conditions, for example, at a temperature and pressure that facilitates the formation of a CEM containing material AB. May be good. The source of the precursor may be, for example, AB or A and B from separate "targets", and the deposition may be an atom or molecule or the mean free path of A or B or AB approximately from the target to the substrate. Material A or B, either physically or thermally, or by other means, in a process chamber that is low enough to reach or be longer than this distance, or lower than this sufficient pressure. Alternatively, it is taken from a target composed of AB (sputtered) and is brought about using the flow of atoms or molecules contained in the "line of sight" of the substrate. AB (or A or B) or both flows so as to form AB on the substrate under conditions of reaction chamber pressure, substrate temperature and other properties controlled by those skilled in the art of PVD and sputter growth. Can be together. In PVD or other embodiments of sputtered growth, the ambient environment may be a source such as BY, or sputtered nickel for forming nitrogen seed-doped NiOs such as, for example, _NH3 . Peripheral NH ₃ may be used for the purpose of the reaction of. The PVD film and the modified form of the PVD film are deposited with a thickness and characteristic correlated electronic material that can show the ratio of the first impedance state to the second impedance state, which is at least 5.0: 1.0. Until then, continue for the required time under conditions as determined by those skilled in the art of PVD.

In a plurality of embodiments, a single nitrogen-containing precursor as shown in the exemplary molecule of FIG. 12A is utilized in place of a mixture of gaseous precursors such as AX and nitrogen-based gases. , Correlated electronic material devices may be manufactured. FIG. 12A is a diagram of nickel aminated Ni (AMD) that can function as a precursor used in the fabrication of correlated electronic material devices according to one embodiment 1201. As shown in FIG. 12A, the nickel atom near the center of the Ni (AMD) molecule is surrounded by four nitrogen atoms, one or more of the four nitrogen atoms being hydrocarbons. It may be attached to a group (represented by "R" in FIG. 12A). Suitable hydrocarbon groups are, but are not limited to, C ₁ to C ₆ linear and branched alkyl groups such as isopropyl group (C ₃ H ₇ ), isobutyl group (C ₄ H ₉ ) or methyl. The group (CH ₃ ) can be mentioned. In certain embodiments, Ni (AMD) can be utilized as the precursor AX, eliminating the need to utilize separate nitrogen-based gases such as AX and ammonia. In certain embodiments, oxidation such as oxidation that may occur in response to exposure to precursor BY, for example, can release nitrogen atoms so that they can function as electron-donating or back-donating positive materials. ..

In another embodiment, nitrogen-containing precursors as shown in the exemplary molecule of FIG. 12B replace gaseous precursors such as AX and nitrogen-based gases in the fabrication of correlated electronic material devices. It may be used. For example, as shown in the exemplary molecule of FIG. 12B (Embodiment 1202), nickel 2-aminopenta-2-en-4-onato (Ni (apo) ₂ ) may be utilized as the precursor AX. This eliminates the need to utilize separate nitrogen-based gases such as AX and ammonia. As shown in the exemplary molecule of FIG. 12B (Embodiment 1202), nitrogen can be supplied by two nitrogen atoms located near the center of _two Ni (apo) molecules. In certain embodiments, oxidation such as oxidation that may occur in response to exposure to precursor BY, for example, can release nitrogen atoms so that they can function as electron-donating or back-donating positive materials. ..

13A-13D show the sub-processes used in the method for making a film comprising CEM according to one embodiment. The subprocesses of FIGS. 13A to 13D utilize gases mainly composed of the precursors AX, BY and nitrogen of the formula (6b) (ammonia (NH ₃ ), ethylenediamine (C ₂ H ₈ N ₂ ), etc.). NiO: Can accommodate atomic layer growth processes in which the components of NH ₃ can be deposited on a conductive substrate. However, by substituting the material for a suitable material, the subprocesses of FIGS. 13A-13D are used to make films containing other transition metals, transition metal compounds, transition metal oxides or CEMs utilizing combinations thereof. However, the subject matter claimed is not limited in this regard.

As presented in FIG. 13A (Embodiment 1301), a substrate such as substrate 1350 may have a gaseous nickel di (cyclopentadienyl) (cyclopentadienyl) over a duration ranging from, for example, approximately 1.0 to 120.0 seconds. Precursor of formula (6a) which may contain Ni (Cp) ₂ ), gaseous nickel aminate (Ni (AMD)) and / or gaseous nickel 2-aminopent-2-en-4-onato. It may be exposed to a first gaseous precursor such as AX. In one embodiment according to formula (6b), the precursor AX may be accompanied by a nitrogen-containing precursor such as ammonia (NH ₃ ), ethylenediamine (C ₂ H ₈ N ₂ ) or other nitrogen-containing ligand. As mentioned above, the atomic concentration and exposure time of the first gaseous precursor is, for example, between approximately 0.1% and 10.0% in the produced correlated electronic material, the final atomic concentration of nitrogen. Can be adjusted to bring about.

As shown in FIG. 13A, exposure of the substrate to, for example, a mixture of gaseous nickel di (cyclopentadienyl) (Ni (Cp) ₂ ) and gaseous ammonia (NH ₃ ) is the surface of the substrate 1350. _Two molecules of Ni (Cp) can be attached at various locations. In a plurality of embodiments, such adhesion or deposition of Ni (Cp) ₂ and ammonia (NH ₃ ) can reach temperatures ranging from, for example, approximately 20.0 ° C to 400.0 ° C, in a heated chamber. Can be carried out within. However, it should be noted that further temperature ranges are possible, such as temperature ranges below approximately 20.0 ° C and above approximately 400.0 ° C, and the claimed subject matter is not limited in this regard. A gaseous precursor containing Ni (AMD) (an exemplary molecule shown in FIG. 12A) and / or Ni (apo) ₂ (an exemplary molecule shown in FIG. 12B) is gaseous Ni (Cp). It should be noted that it may be used in place of a mixture of ₂ and gaseous ammonia (NH ₃ ).

As shown in FIG. 13B (Embodiment 1302), the conductivity of a conductive substrate such as 1350 is exposed to a gaseous precursor such as a mixture of gaseous precursors containing Ni (Cp) ₂ and ammonia (NH ₃ ). After that, the chamber can purge residual gaseous Ni (Cp) ₂ , Cp ligands and unbound ammonia molecules. In one embodiment, for an example of a gaseous precursor containing a gaseous mixture of Ni (Cp) ₂ and NH ₃ , the chamber is purged for a duration ranging from approximately 5.0 seconds to 180.0 seconds. be able to. In one or more embodiments, the purge duration depends, for example, on the affinity (excluding chemical bonds) of unreacted ligands and / or unreacted ammonia molecules with transition metals or transition metal oxides and the like. obtain. Thus, for the example of FIG. 13B, if the unreacted Cp and / or unreacted ammonia molecules exhibit increased affinity for Ni, the longer purge duration is utilized to take advantage of the Cp ligand, etc. The residual gaseous ligand of the above may be removed, and further, unreacted ammonia may be removed. In other embodiments, the purge duration may depend, for example, on the gas flow in the chamber. For example, a gas flow in a chamber where laminar flow is dominant can remove residual gaseous ligands and / or ammonia at a faster rate, but a gas flow in a chamber where turbulence is dominant. Can remove the residual ligand at a slower rate. It should be noted that the claimed subject matter is intended to include purging residual gaseous material, which can increase or decrease the rate at which gaseous material is removed, regardless of the flow characteristics within the chamber. be.

As presented in FIG. 13C (Embodiment 1303), a second gaseous precursor such as the precursor BY of formulas (6a) and (6b) can be introduced into the chamber. As mentioned above, the second gaseous precursor may contain an oxidant, which dispels one or more first ligands, such as Cp, in some examples. Oxidizing agents such as oxygen (O ₂ ), ozone (O ₃ ), nitrogen monoxide (NO), and hydrogen peroxide (H ₂ O ₂ ) can act to replace the ligand. Thus, as shown in FIG. 13C, the oxygen atom, for example, in addition to pushing away a relatively small number of ammonia (NH ₃ ), is between at least some nickel atoms bonded to the substrate 1350. Bonds can be formed. In one embodiment, the precursor BY is the following formula (12).
Ni (C ₅ H ₅ ) ₂ + O ₃ → NiO +
Possible by-products (eg CO, CO ₂ , C ₅ H ₅ , C ₅ H ₆ , CH ₃ , CH ₄ , C ₂ H ₅ , C ₂ H ₆ , NH ₃ ...) (12)
(In this case, C ₅ H ₅ replaced Cp in formula (12)) to oxidize Ni (Cp) ₂ to form some additional oxidants and / or combinations thereof. be able to. FIG. 4C shows some possible by-products including C ₂ H ₅ , CO ₂ , CH ₄ and C ₅ H ₆ . Similarly, as shown in FIG. 13C, ammonia (NH ₃ ) can remain bound to the nickel oxide complex, for example at site 1360 in 1361. In a plurality of embodiments, such nickel-ammonia bonds (eg, NiO: NH ₃ ) are at atomic concentrations, eg, between 0.1% and 10.0%, in the manufactured CEM device. It may allow electron donation or back donation which can result in substantially rapid conductor / insulator transitions for CEM devices.

As shown in FIG. 13D (Embodiment 1304), for example, in addition to unreacted ammonia, CO, CO ₂ , C ₅ H ₅ , C ₅ H ₆ , CH ₃ , CH ₄ , C ₂ H ₅ , C ₂ Possible hydrocarbon by _- products such as H6 can be purged from the chamber. In certain embodiments, such chamber purging is performed utilizing a pressure in the range of approximately 0.25 Pa to 100.0 kPa over a duration in the range of approximately 5.0 to 180.0 seconds. Can be done.

In certain embodiments, the subprocesses described in FIGS. 13A-13D can be repeated until a desired thickness of correlated electron material, such as a thickness in the range of approximately 200.0 Å to 1000.0 Å, is achieved. can. As mentioned above in the present specification, atomic layer growth methods such as those presented and described with reference to FIGS. 13A-13D are CEMs occupying thicknesses ranging from, for example, approximately 0.6 Å to 1.5 Å. A device film can be produced. Therefore, in order to construct a CEM device film that occupies a thickness of 500.0 Å, for example, AX _gas + (NH ₃ or another ligand containing nitrogen) + BY _gas is used as a mere possible example of about 300. Up to 900 cycles with the two precursors may be performed. In certain embodiments, the cycle can sometimes be interrupted between different transition metals and / or transition metal oxides to obtain the desired properties. For example, in one embodiment, two atomic layer growth cycles in which a layer of NiO: NH ₃ can be formed, for example, three atoms for forming a complex of titanium oxide and ammonia (TiO: NH ₃ ). A layer growth cycle may follow. Other interrupts of transition metals and / or transition metal oxides are also possible and the claimed subject matter is not limited in this regard.

In certain embodiments, after completion of one or more atomic layer growth cycles, the substrate can be annealed, which can assist in controlling the grain structure. For example, if atomic layer growth yields a number of columnar grains, annealing allows the boundaries of the columnar grains to grow together, which boundaries are, for example, relatively high impedance in CEM devices, for example. The resistance of the state can be reduced and / or the current capacity can be improved. Annealing can provide additional benefits, such as more uniform distribution of nitrogen molecules such as ammonia throughout the CEM device material, and the claimed subject matter is not limited in this regard.

In a plurality of embodiments, the CEM device containing the nitrogen-containing dopant utilizes the precursor flow profile presented and described with respect to FIGS. 9A-9D and the temperature profile presented and described with reference to FIGS. 10A-10C. Can be manufactured.

14 to 18 are flow charts of embodiments of a further method for making correlated electronic materials. The method of FIG. 14 (Embodiment 1400) may be initiated in block 1410, which may include the step of depositing a film containing a d-block element such as Ni or an f-block element. In a plurality of embodiments, the deposition step is, for example, PVD (eg, plasma may be included and / or reactive gas may be included, sputtering), CVD, MOCVD, ALD, gas cluster ion. Beam (GCIB) growth, plasma ALD, plasma CVD and plasma MOCVD may be included. The method of FIG. 14 may remain in block 1420, which may oxidize, for example, Ni to form, for example, NiO, or O ₂ , O ₃ , O *, H ₂ O, NO, N. ₂ A film containing a d-block element or f-block element and a dominant ligand by oxidation or oxynitride using an O or NO * source (where "*" includes any integer). May include a step of forming. In block 1420, the film is, for example, O ₂ ^2- (peroxide), I- ⁽ iodide ion), ^{Br- (odoride ion), S 2- (} sulfur), SCN- (thiocyanide ion, [SCN ^{]- (} Sulfur-carbon-nitrogen ligand with carbon in between), ^Cl- (chloride ion), N3 _- azido ^, F- ⁽ fluoride ion), ^NCO- (cyanide), OH- ⁽ hydroxy) D), C ₂ O ₄ ^2- oxalate, H ₂ O (water), ^NCS- (isothiocyanate), CH ₃ CN (acetriform), C ₅ H ₅ N (py or pyridine), NH ₃ , ethylenediamine (C ₂ ). H ₄ (NH ₂ ) ₂ ), bipy (2,2'-bipyridine), C ₁₀ H ₈ N ₂ (phenanthroline), C ₁₂ H ₈ N ₂ (phenanthroline), NO _2- ⁽ The molecular dopant may be doped with a molecular dopant such as nitrogen), PPh ₃ (triphenylphosphine or P (C ₆ H ₅ ) ₃ ), CN- (cyanide ion) and spectral series ligands such as CO. , C _{x Hy} Oz (where x, y and z are integers and at least x or y or z is ≧ 1), C _{x Hy} N _z (in the formula, x, y and _z ). z is an integer and at least x or y or z is ≧ 1) and N _x Oy (in the equation, x and _y are integers and at least x or y is ≧ 1). It may contain a hydrocarbon such as a molecule of the above, a carbonate, a hydroxide, and a nitrogen complex.

Oxidation or nitridation may be carried out at a pressure in the range of approximately 0.01 kPa to 800.0 kPa and a temperature in the range of 20.0 ° C to 1100.0 ° C. In certain embodiments, oxidation or nitridation may be carried out at temperatures in the range of approximately 50.0 ° C to 900.0 ° C. In certain embodiments, oxidation or oxynitride can be carried out over a time period ranging from 1.0 second to 5.0 hours, whereas in certain embodiments it is approximately 1.0 second to 60 seconds. It may be carried out within a range of 0.0 minutes. In block 1430, the CEM film may be doped with a dopant ligand, such as by utilizing a carbon-based source such as methane (CH ₄ ). At block 1440, the film can be annealed to form a particular dopant species, such as CO or NH ₃ . Annealing at high temperatures or annealing at the same or lower temperatures than the deposition temperature can be performed utilizing temperatures in the range of approximately 20.0 ° C ( _low T) to 900.0 ° C ( _high T). .. However, in certain embodiments, a narrower range, such as a temperature range in the range of approximately 100.0 ° C. (T _low ) to 800.0 ° C. (T _high ), may be utilized. At block 1450, further annealing can be performed using temperatures similar to those used at block 1440, but at least in certain embodiments, different temperature ranges may be used. Annealing at block 1450 can act to move a particular dopant species molecule (such as CO or NH ₃ ) to the atom of the d-block element or f-block element.

The method of FIG. 15 (Embodiment 1500) may be initiated in block 1510, where the block 1510 is dominant such that a coordination sphere such as a d-block element such as Ni or an f-block element and NiO is formed. It may include a step of depositing a film, including a ligand. In certain embodiments, the coordination sphere may include empty lattice points of the dominant ligand, such as oxygen empty lattice points. At block 1520, the film may be doped with molecular dopants such as those described for block 1420, such as spectral sequence ligands. At block 1530, the film can be annealed to form a particular dopant species such as CO or _NH3 . At block 1540, the film can be annealed to transfer a particular dopant species, such as CO or NH ₃ , to a d-block element atom or an f-block element atom.

The method of FIG. 16 (Embodiment 1600) may be initiated in block 1610, wherein the block 1610 is a d-block element such as Ni or an f-block element and a block so that the dopant species are incorporated into the film. It may include the step of depositing a film containing a molecular dopant such as that described for 1420. In a plurality of embodiments, the dopant species incorporated into the film can form a dopant ligand, such as an organic ligand, in the MOCVD process. The MOVCD process with an organic ligand is a β-diketonate-type ligand such as bis (2,4-pentandionato) or acetylacetonato (acac), 1,1,1,5,5,5-hexafluoro. Acetylacetonato (hfac), 2,2,6,6-tetramethyl-3,5,-heptandionato (thd), cyclopentadienyl (Cp) and ethyl and methyl derivatives (MeCp) of cyclopentadienyl, Cyclopentadienyl-type ligands such as (CpEt) and alkoxy-based ligands such as ethoxy (OEt), methoxy (OMe) and isopropoxy (OiPr) can be utilized. At block 1630, the film can be annealed to move a particular dopant species, such as CO or NH ₃ , to a d-block element atom or an f-block element atom (Ni, etc.).

The method of FIG. 17 (Embodiment 1700) may be initiated in block 1710, which comprises a d-block element such as Ni or an f-block element and a block so that the dopant species are incorporated into the film. It may include the step of depositing a film containing a molecular dopant such as that described for 1420. In multiple embodiments, the dopant species incorporated into the film may be capable of forming dopant ligands (such as organic ligands in the MOCVD process). At block 1720, the film can be annealed to transfer a particular dopant species, such as CO or NH ₃ , to a d-block element atom (such as Ni) or an f-block element atom.

The method of FIG. 18 (Embodiment 1800) may include block 1810, which comprises a d-block element or f-block element in the coordination sphere containing the major bond to the dominant ligand. It may include a step of depositing. The coordination sphere may include, to a lesser extent, a bond to a molecular dopant, such as the molecular dopant described for block 1420. The block 1820, which can be performed during the operation of the CEM device, may include steps that allow the movement of electrons into and out of the molecular energy level to result in CEM behavior. Such behavior may include switching between a low impedance state and a high impedance state of the CEM device.

In certain embodiments, the CEM device can be implemented in any of a wide variety of integrated circuit types. For example, in one embodiment, many CEM devices can be implemented in an integrated circuit to form a programmable memory array, where the programmable memory array is, for example, the impedance state of one or more CEM devices. It can be reconstructed by making changes. In another embodiment, the programmable CEM device can be utilized, for example, as a non-volatile memory array. Of course, the claimed subject matter is not limited in scope to the specific examples provided herein.

To provide an integrated circuit device, the plurality of CEM devices may include, for example, a first correlated electronic device having a first correlated electronic material and a second correlated electronic device having a second correlated electronic material. The first correlated electron material and the second correlated electron material that can be formed can have substantially different impedance characteristics. Further, in one embodiment, a first CEM device and a second CEM device having different impedance characteristics from each other can be formed in a specific layer of an integrated circuit. Further, in one embodiment, forming a first CEM device and a second CEM device in a particular layer of an integrated circuit can at least partially form the CEM device by selective epitaxial deposition. It may be included. In another embodiment, the first CEM device and the second CEM device in a particular layer of the integrated circuit at least partially, eg, the impedance characteristics of the first CEM device and / or the second CEM device. It may be formed by an ion implantation that modifies it.

Further, in one embodiment, two or more CEM devices can be formed, at least in part, in a particular layer of an integrated circuit by atomic layer deposition of correlated electronic materials. In a further embodiment, one or more of the plurality of correlated electronic switch devices of the first correlated electronic switch material and one or more of the plurality of correlated electronic switch devices of the second correlated electronic switch material. At least in part, it can be formed by a combination of blanket deposition and selective epitaxial deposition. Further, in one embodiment, the first access device and the second access device may be positioned substantially adjacent to the first CEM device and the second CEM device, respectively.

In a further embodiment, one or more of the plurality of CEM devices is one of a conductive wire of a first metallized layer and a conductive wire of a second metallized layer in one embodiment in an integrated circuit. They may be individually located at one or more intersections. The one or more access devices may be located at one or more of the intersections of the conductive wire of the first metallized layer and the conductive wire of the second metallized layer. , In one embodiment, it may be paired with each CEM device.

In the above description, being "above" and "covering" in the particular context of use, such as in situations where tangible components (and / or similarly, tangible materials) are discussed. There is a distinction between them. As an example, the deposition of material on the substrate "on" is based on the material on which inclusions such as inclusions (eg, inclusions formed during the operation of intervening processes) in this example are deposited. Refers to sedimentation with tangible physical direct contact, not between materials. However, deposits that "cover" the substrate potentially include deposition on the substrate "above" (because "above" is, strictly speaking, "covering". While it is understood (because it may have been described), one or more of the deposited material is not necessarily in tangible physical direct contact with the substrate. It is also understood to include situations where one or more inclusions, such as multiple inclusions, are present between the deposited material and the substrate.

A similar distinction is made between "underneath" and "below" in the appropriate specific context for use, such as in the context in which tangible materials and / or tangible components are discussed. To. In the particular context of such use, "below" is intended to always imply tangible physical contact (similar to "above" above), while "below" is tangible. Possibly including situations where physical direct contact is present, but suggesting tangible physical direct contact in the presence of one or more inclusions, such as one or more inclusions, etc. Is not always. Therefore, "above" is understood to mean "immediately above" and "just below" is understood to mean "immediately below".

It is also understood that terms such as "covering" and "bottom" are understood in the same manner as the terms "top", "bottom", "top" and "bottom" described above. These terms can be used to facilitate the discourse, but are not intended to necessarily limit the scope of the claimed subject matter. As an example, the term "covering" is used, for example, when the scope of the claim is compared with, for example, an upside-down state of the embodiment, with the embodiment facing up. It is not understood to suggest that it is limited to only certain situations. One example includes flip chips, for example, where orientation at various times (eg, in production) may not necessarily correspond to the orientation of the final product. Therefore, if an object, as an example, is included in the scope of applicable claims in a specific oriented state, such as an upside down state, which is also an example, the wording of the applicable verbatim claim. An object in this state is also, as an example, another orientation, such as a front-side up state and vice versa, even when it may be interpreted as otherwise. It is intended to be construed as being included in the scope of applicable claims. Of course, again, as has always been the case with the specification of a patent application, the particular context of description and / or use provides useful guidance for rational reasoning to be derived.

Unless otherwise indicated, the term "or" as used in the context of this disclosure in connection with a list such as A, B or C is used herein in a comprehensive sense. When used, it is intended to mean A, B and C, and further, when used in an exclusive sense here, it is intended to mean A, B or C. There is. When understood in this way, "and" is used in a comprehensive sense and is intended to mean A, B and C, but "and / or" is a great deal of caution. Can be used to clarify that all of the above meanings are intended, but such use is not required. In addition, the term "one or more" and / or similar terms are used to describe any singular feature, structure and / or property, etc., where "and / or" are plural and / or. / Or also used to describe the characteristics, structure and / or characteristics of some other combination. In addition, terms such as "first," "second," and "third" imply numerical limits or suggest a particular order, unless explicitly indicated otherwise. Instead, it is used as an example to distinguish different aspects such as different components. Similarly, the term "based" and / or similar terms are not necessarily intended to imply elements of an exclusive list, and there are additional elements that are not always explicitly stated. It is understood as intended to be acceptable.

Further, with respect to the embodiment of the claimed subject matter, the situation of being tested, measured and / or designated with respect is intended to be understood as follows. As an example, assume that the value of a physical property should be measured in a given situation. Continuing this example, it is reasonably possible that a person skilled in the art would come up with a reasonable alternative to testing, measuring and / or specifying, at least for the degree, at least for the purpose of implementation. In some cases, the claimed subject matter is intended to include reasonable approaches to these alternatives, unless explicitly indicated otherwise. As an example, a plot of measurements over a region is generated, and the patented subject matter implementation relates to adopting a tilt measurement over the region, but various to estimate the tilt over the region. Where rational and alternative techniques exist, the claimed subject matter is, even when these rational and alternative techniques do not yield the same values, the same measurements or the same results. Unless explicitly indicated otherwise, it is intended to include these rational and alternative techniques.

When used with features, structures and / or properties, etc., when using "optical" or "electrical" as a simple example, the terms "mold" and / or "like" are not trivial. In some cases, the presence of minor changes is generally a minor change, even if it is a change that may not be considered to be in perfect agreement with the characteristics, structure and / or characteristics, etc. If, if still present, the features, structures and / or properties are light enough to be considered to still predominantly exist, then the features, structures and / or properties, etc. are "type" and / Or means at least a part of a feature, structure and / or characteristic, etc., in such a manner that it does not prevent it from being "like" (for example, being "optical" or "optical"). And / or further note that it means about features, structures and / or properties, etc. Therefore, continuing this example, the terms optical type properties and / or optical-like properties are intended to always include optical properties. Similarly, as another example, the terms electrical and / or electrical-like properties are intended to always include electrical properties. It should be noted that the designations in this disclosure provide one or more explanatory examples, and the claimed subject matter is intended not to be limited to one or more explanatory examples. Should be. However, again, as has always been the case with the specification of a patent application, the particular context of description and / or use provides useful guidance for rational reasoning to be derived.

In the above description, various embodiments of the claimed subject matter have been described. For purposes of illustration, details such as quantity system and / or configuration are provided as examples. In other cases, well-known features have been omitted and / or simplified so as not to interfere with the claimed subject matter. Although specific features have been exemplified and / or described herein, a number of modifications, substitutions, modifications and / or equivalents will be conceived by those of skill in the art. Therefore, it should be understood that the appended claims are intended to include all modifications and / or modifications belonging to the claimed subject matter.

100 Embodiment 104 Area of voltage compared to current density profile 108 points 110 Voltage range that can separate V _set from V _reset 116 points 122 Device terminal 126 Variable resistor 128 Variable capacitor 130 Device terminal 150 Embodiment 160 Conductivity Base material 170 CEM film 180 Conductive base material 200 Embodiment 210 Conductive base material 220 Transition metal oxide film 230 Filament 240 Conductive overlay 240 Block 300 Embodiment 310 σ bond 320 Embodiment 322 π bond 324 π bond 335 Ni D-orbital of atom 337 d-orbital of Ni atom 340 Embodiment 360 Embodiment 380 NiO complex 385 NiO complex 390 Ni atom 391 Ni atom 395 Oxygen empty lattice point 397 CO ligand 398 NH ₃ ligand 400 Embodiment 410 Conduction band 420 valence band 450 embodiment 460 conduction band 470 valence band 500 embodiment 510 block 520 block 601 embodiment 602 embodiment 603 embodiment 610 block 620 block 630 block 640 block 650 block 660 block 671 block 672 block 673 block 700 800 Embodiment 810 Embodiment 820 Embodiment 830 Embodiment 850 Substrate 860 Site 861 Site 901 Embodiment 902 Embodiment 903 Embodiment 904 Embodiment 907 Embodiment 908 Embodiment 910 Precursor gas flow profile 920 Purge gas gas flow profile 930 Gas flow profile of the precursor gas 940 Embodiment 950 Embodiment 1000 Embodiment 1001 Embodiment 1002 Embodiment 1101 Embodiment 1102 Embodiment 1103 Embodiment 1110 block 1120 block 1130 block 1140 block 1150 block 1160 block 1162 block 1164 block 1166 block 1168 block 1170 block 1201 embodiment 1202 embodiment 1301 embodiment 1302 embodiment 1303 embodiment 1304 embodiment Condition 1350 Base material 1360 Site 1361 Site 1400 Example 1410 block 1420 block 1430 block 1440 block 1450 block 1500 Embodiment 1510 block 1520 block 1530 block 1540 block 1600 Embodiment 1610 block 1620 block 1630 block 1700 embodiment 1710 block Form 1810 block 1820 block

Claims (12)

In the chamber, during the first deposition period, the step of exposing the substrate to one or more gases, including transition metal oxides or transition metals or any combination thereof and a first ligand. So that one or more gases result in an atomic concentration of nitrogen between 0.1% and 10.0% in the produced electron back-donating and substantially bulk switch correlated electronic material. Steps Containing Ligand Atomic Concentrations Containing Nitrogens, a step of exposing a substrate to a gaseous oxide during the first deposition period to form at least a first layer of a film of correlated electronic material.
The step of annealing the exposed substrate during the first annealing period,
Following the first annealing period, during the second deposition period, at least one additional layer of film of correlated electronic material exhibiting a first impedance state and a second impedance state that are substantially different from each other. Repeated steps of exposing the substrate to one or more gases and gaseous oxides to form, and
In the step of annealing the exposed substrate during the second annealing period, additional material is at least partially introduced into the film of the correlated electron material to provide electron back donation in the film of the correlated electron material. Promote, process,
How to include. Correlation electronic materials of electron back donation and substantially bulk switch are ammonia (NH ₃ ), ethylenediamine (C ₂ H ₈ N ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ) ^, NO _3- The method of claim 1 , comprising a ligand, an amine, an amide or an alkylamide or any combination thereof. The method of claim 1 or 2 , further comprising purging the chamber of one or more gases for 5.0 to 180.0 seconds during the first deposition period. Any of claims 1 to 3 , wherein the step of exposing the substrate to one or more gases during the first deposition period is performed over a duration between 5.0 and 180.0 seconds. The method described in item 1. The method according to any one of claims 1 to 4 , further comprising repeating the step of exposing the substrate between 50 and 900 times during the first deposition period. Claims 1 to 5 , further comprising repeating the step of exposing the substrate until the film thickness of the correlated electronic material reaches between 1.5 nm and 150.0 nm during the first deposition period. The method described in any one of the items. One or more gases are nickel aminate (Ni (AMD)), nickel di (cyclopentadienyl) (Ni (Cp) ₂ ), nickel di (ethylcyclopentadienyl) (Ni (EtCp)) in a gaseous state. ₂ ), bis (2,2,6,6-tetramethylheptane-3,5-dionat) Ni (II) (Ni (thd) ₂ ), nickel acetylacetonate (Ni (acac) ₂ ), bis (methyl) Cyclopentadienyl) Nickel (Ni (CH ₃ C ₅ H ₄ ) ₂ ), Nickel Dimethyl Glyoxymate (Ni (dmg) ₂ ), Nickel 2-Amino-Penta-2-en-4-onato (Ni (apo) ₂ ), Ni (dmamb) ₂ (in the formula, dmamb = 1-dimethylamino-2-methyl-2-butanolate), Ni (dmamp) ₂ (in the formula, dmamp = 1-dimethylamino-2-methyl-2) -Propanolate), bis (pentamethylcyclopentadienyl) nickel (Ni (C ₅ (CH ₃ ) 5) ₂ ) or nickel carbonyl (Ni (CO) ₄ ) or any combination thereof, according to claim 1 . The method according to any one of 6 . The gaseous oxides are oxygen (O ₂ ), ozone (O ₃ ), water (H ₂ O), nitric oxide (NO), nitrous oxide (N ₂ O) or hydrogen peroxide (H ₂ O ₂ ). Or the method according to any one of claims 1 to 7 , comprising one or more of any combination thereof. During the first deposition period, the step of exposing the substrate to one or more gases and the step of exposing the substrate to gaseous oxides at a temperature between 20.0 ° C and 1000.0 ° C. The method according to any one of claims 1 to 8 , which is carried out. The method of any one of claims 1-9 , wherein the step of annealing the exposed substrate during the second annealing period comprises the step of annealing the exposed substrate in a chamber. 10. The tenth aspect of the invention further comprises the step of raising the temperature of the chamber between 20.0 ° C. and 900.0 ° C. before initiating the annealing of the exposed substrate during the first annealing period. the method of. The exposed substrate is gaseous nitrogen (N ₂ ), hydrogen (H ₂ ), oxygen (O ₂ ), water or water vapor (H ₂ O), nitric oxide (NO), nitric oxide (N ₂ O). ), Nitrogen dioxide (NO ₂ ), Ozone (O ₃ ), Argon (Ar), Helium (He), Ammonia (NH ₃ ), Carbon monoxide (CO), Methan (CH ₄ ), Acetylene (C ₂ H ₂ ) ), Etan (C ₂ H ₆ ), Propane (C ₃ H ₈ ), Ethylene (C ₂ H ₄ ) or Butane (C ₄ H ₁₀ ) or any combination thereof in an environment containing one or more of them. The method according to any one of claims 1 to 11 , wherein the method is annealing during the second annealing period.

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